TW201800434A - Block copolymers with linear surface-active junction groups, compositions and processes thereof - Google Patents

Abstract

The present invention relates to a novel block copolymer having the structure (1a) or (1b): wherein X is a fluorine containing moiety, a Si1-Si8 siloxane containing moiety or a hydrocarbon moiety with at least 18 carbons, and all other variables are as defined herein.

Description

Block copolymer with linear surface active bonding group and composition thereof and preparation method thereof

The present invention relates to a novel block copolymer comprising a bonding group between two blocks, wherein the bonding group has a low surface energy; a novel composition comprising the novel block copolymer and the use of the novel composition Vertical domains (e.g., sheets, cylinders, etc.) are formed by self-assembly (SA) or guided self-assembly (DSA) of the novel block copolymers (BCP). These methods can be used to make electronic devices.

In conventional lithography methods, ultraviolet (UV) radiation can be used to expose a photoresist layer applied to a substrate or layered substrate via a mask. Positive or negative photoresists are useful, and such photoresists may also contain a refractory element (e.g., ruthenium) to enable dry development using conventional integrated circuit (IC) plasma processing. In a positive photoresist, the UV radiation transmitted through the mask causes a photochemical reaction in the photoresist such that the exposed areas are removed using a developer solution or by conventional IC plasma treatment. In contrast, in a negative photoresist, the UV radiation transmitted through the mask makes it less likely that the area exposed to the radiation will be removed by the developer solution or by conventional IC plasma treatment. The integrated circuit features (such as gates, vias, or interconnects) are then etched into the substrate or layered substrate and the remaining photoresist removed. When using the conventional lithography exposure method, the feature size of the integrated circuit features is limited. Further reduction in pattern size is difficult to achieve with radiation exposure due to limitations associated with aberrations, focusing, proximity effects, minimum achievable exposure wavelengths, and maximum achievable numerical aperture. Guided self-assembly is a promising approach that is of concern in overcoming some of the shortcomings of conventional lithography as outlined above. In particular, a guided self-assembly of block copolymers can be used to create micropatterned features to fabricate microelectronic devices in which the feature size is typically in the range of 10 nm to 50 nm, typically on the nanometer scale. The critical dimension of the feature (CD). It is challenging to achieve a feature size of less than 10 nm using conventional methods of guided self-assembling block copolymers. Guided self-assembly methods that extend the analytical capabilities of lithography, such as those based on block copolymers and chemical epitaxy. These techniques can be employed to enhance conventional lithography by enabling CD control with higher resolution patterns and/or improved EUV, electron beam, deep UV or immersion lithography. The guided self-assembling block copolymer comprises blocks of etch resistant copolymerization units and blocks of highly etchable copolymerization units that produce regions with high resolution patterns when coated, aligned, and etched onto the substrate. For example, known examples of block copolymers suitable for guided self-assembly are those which are capable of microphase separation and which contain a plasma-resistant block that is resistant to plasma etching (for example styrene or contains some other elements such as Si, Ge and Ti) and highly plasma etchable or removable blocks that provide high resolution pattern definition. Examples of highly etchable blocks can include monomers that are rich in oxygen and that are free of refractory elements and that are capable of forming highly etchable blocks, such as methyl methacrylate. The plasma etching gases used in the etching process for defining self-assembled patterns are generally used in the fabrication of integrated circuits (ICs). In this way, a very fine pattern can be produced on a typical IC substrate as compared to conventional lithography, thereby achieving pattern enlargement. In the patterned epitaxial guided self-assembly method, the block copolymer is self-organized on a substrate which is pre-patterned by conventional lithography (ultraviolet, deep UV and electron beam, extreme ultraviolet (EUV) exposure sources). Topographical features are formed, such as line/space (L/S) or contact hole (CH) patterns. In an example of an L/S guided self-assembled array, the block copolymer can form a self-aligned flaky region having a sub-picographic pitch in the trench between the sidewalls of the pre-pattern, thereby by morphing The space in the trench between the lines is subdivided into finer patterns to enhance pattern resolution. Similarly, features such as contact holes can be made denser by using a patterning epitaxy method in which a suitable block copolymer is guided by an array of pre-patterned holes or pre-patterned columns defined by conventional lithography. Self-assembly self-configuring, thereby forming a denser array of etchable regions and etch-resistant domains that produce a denser array of contact holes upon etching. Additionally, the block copolymer can form a single and small etchable domain at the center of the pre-patterned pores of appropriate size and provide potential shrinkage and correction of the pores in the pre-pattern. Therefore, the pattern epitaxy has the potential to provide pattern correction and pattern enlargement. In the chemical epitaxial DSA process, the self-assembly of the block copolymer is carried out on the surface of a region having different chemical affinities but no morphology or having a very slight morphology to guide the self-assembly process. For example, chemical pre-patterns can be made using lithography (UV, deep UV, electron beam, EUV) and nanofabrication methods to produce surfaces with different chemical affinities in the in-line and space (L/S) patterns. These regions can exhibit very few morphological differences to no morphological differences, but exhibit surface chemical patterns to direct self-assembly of the block copolymer domains. This technique allows for the precise placement of such block copolymer domains having a spatial frequency higher than the spatial frequency of the pre-pattern. After the plasma or wet etch process, the aligned block copolymer domain pattern can then be transferred to the underlying substrate. In addition, chemical epitaxy has the following advantages: block copolymer self-assembly can correct the surface chemistry, size and roughness of the underlying chemical pattern to obtain improved line edge roughness in the final self-assembled block copolymer domain pattern. Degree and CD control. Other types of patterns, such as contact hole (CH) arrays, can also be generated or corrected using chemical epitaxy. The ability to phase separate BCP depends on the Flory Huggins interaction parameter (χ). PS-b-PMMA (poly(styrene-block-methyl methacrylate) is the most promising candidate for guided self-assembly (DSA) applications. However, due to the interaction parameters between PS and PMMA (χ Lower), the minimum half pitch of PS-b-PMMA is limited to about 10 nm. For further feature miniaturization, block copolymerization with high interaction parameters (higher enthalpy) between two blocks is highly desirable. For lithography applications, it is desirable for the block copolymer domain to be oriented perpendicular to the substrate. For two blocks with a similar surface energy at the BCP-air interface, a conventional block copolymer (eg PS-b-PMMA) This can be achieved by coating the block copolymer on a layer of a non-preferential or neutral material grafted or crosslinked at the polymer-substrate interface and thermally annealing it. Due to the higher c block copolymerization The large difference in the interaction parameters between the domains, it is important to control the interaction between BCP-air and BCP-substrate. Many orientation control strategies for generating vertically oriented BCP domains have been implemented using BCP with higher c. For example, solvent vapor annealing has been used to orientate polystyrene-b-polycyclic rings. Ethane (PS-b-PEO), polystyrene-b-polydimethyloxane (PS-b-PDMS), polystyrene-b-poly(2-vinylpyridine) (PS-b- P2VP), polylactide-b-poly(trimethyldecylstyrene) PLA-b-PTMSS and PαMS-b-PHOST. The kinetics of introducing a solvent vapor chamber and solvent vapor annealing can complicate DSA processing. Alternatively, a combination of neutral underlayer and facing materials has been applied to PS-b-P2VP, PS-b-PTMSS, and PLA-b-PTMSS to achieve vertical orientation of the polymer domain. However, additional facing materials may be added. Manufacturing costs and complexity. Therefore, the industry needs to use a simple thermal annealing on a series of preferential and non-priority substrates to obtain a higher c-free BCP system without a top layer. It consists of A and B blocks and has a perfluoroalkyl group. The synthesis of the diblock copolymer of the pendant group of the pendant group is described in U.S. Patent Application Serial No. 14/628,002, the entire disclosure of which is incorporated herein by reference. The invention relates to novel block copolymers having one or more low surface energy groups at the junction of two blocks. The invention further relates to the inclusion of novel block copolymers The composition, and also relates to a novel process comprising coating a film comprising a novel block copolymer, wherein the process allows the BCP domain to be oriented vertically in a film (5-100 nm) by simple thermal annealing over a suitable substrate. .

(1a) 其中， A係嵌段聚合物鏈， B係嵌段聚合物鏈， 其中A及B係化學上不同之共價連接聚合物鏈，其係相可分離的； X係在A聚合物嵌段與B聚合物嵌段之間選自由以下組成之群之二價鏈接基團：含氟部分、含Si₁ -Si₈ 矽氧烷之部分、具有至少18個碳之烴部分及其組合，且 進一步其中X具有小於嵌段A且小於嵌段B之表面能。 在某些實施例中，嵌段共聚物具有結構(1b)：

(1b) 其中 E¹ 係單價第一末端基團， E² 係單價第二末端基團， P'係代表該嵌段共聚物之第一嵌段(嵌段A)之第一聚合物鏈， P''係代表該嵌段共聚物之第二嵌段(嵌段B)之第二聚合物鏈，且 X係將P’之末端重複單元接合至P''之末端重複單元之二價鏈接基團，其中X包含1-24個氟，且X之該等氟中之每一者鏈接至該嵌段共聚物之骨架碳。 在某些實施例中，嵌段共聚物具有結構(1b)：

(1b) 其中 E¹ 係單價第一末端基團， E² 係單價第二末端基團， P'係代表該嵌段共聚物之第一嵌段(嵌段A)之第一聚合物鏈， P''係代表該嵌段共聚物之第二嵌段(嵌段B)之第二聚合物鏈，且 X係將P’之末端重複單元接合至P''之末端重複單元之二價鏈接基團，其中X包含含有1-24個碳之全氟烷烴，且X係在兩個末端直接或藉助由1-6個碳組成之烷烴間隔體鏈接至該嵌段共聚物之骨架碳。 本發明亦係關於包含新穎嵌段共聚物及溶劑之組合物，且亦係關於將此組合物用於自組裝及引導式自組裝製法中之製法。The present invention relates to novel block copolymers wherein the block copolymers comprise a diblock copolymer having a divalent bonding or linking group (X). The copolymer has a first polymer block (block A) and a second polymer block (block B). In a particular embodiment, block B has a chemical structure different from block A and is capable of segregating from block A. In certain embodiments, the divalent linking group X covalently links the terminal repeating unit of block A to the terminal repeating unit of block B. In certain embodiments, the block copolymer has the structure (1a):

(1a) wherein, A is a block polymer chain, a B-based block polymer chain, wherein A and B are chemically different covalently bonded polymer chains, and the tether phase is separable; X is in A polymer a divalent linking group selected from between the block and the polymer block B of the group consisting of: fluorine-containing moiety, the alkyl portion of the silicon oxide containing Si ₁ -Si _8, having at least 18 carbon composition of the hydrocarbon moiety and And further wherein X has a surface energy less than block A and less than block B. In certain embodiments, the block copolymer has the structure (1b):

(1b) wherein E ¹ is a monovalent first terminal group, E ² is a monovalent second terminal group, and P′ represents a first polymer chain of the first block (block A) of the block copolymer, P'' represents the second polymer chain of the second block (block B) of the block copolymer, and X is a bivalent link linking the terminal repeating unit of P' to the terminal repeating unit of P'' a group wherein X contains 1-24 fluorines, and each of the fluorines of X is linked to the backbone carbon of the block copolymer. In certain embodiments, the block copolymer has the structure (1b):

(1b) wherein E ¹ is a monovalent first terminal group, E ² is a monovalent second terminal group, and P′ represents a first polymer chain of the first block (block A) of the block copolymer, P'' represents the second polymer chain of the second block (block B) of the block copolymer, and X is a bivalent link linking the terminal repeating unit of P' to the terminal repeating unit of P'' a group wherein X comprises a perfluoroalkane containing from 1 to 24 carbons, and the X system is linked to the backbone carbon of the block copolymer either directly or via an alkane spacer consisting of from 1 to 6 carbons at both ends. The present invention is also directed to compositions comprising novel block copolymers and solvents, and also to processes for using such compositions in self-assembly and guided self-assembly processes.

(1a) 其中， A係嵌段聚合物鏈， B係嵌段聚合物鏈， 其中A及B係化學上不同之共價連接聚合物鏈，其係相可分離的； X係在A聚合物嵌段與B聚合物嵌段之間選自由以下組成之群之二價鏈接基團：含氟部分、含Si₁ -Si₈ 矽氧烷之部分、具有至少18個碳之烴部分及其組合，且 進一步其中X具有小於嵌段A且小於嵌段B之表面能。 在某些實施例中，嵌段共聚物具有結構(1b)：

(1b) 其中 E¹ 係單價第一末端基團， E² 係單價第二末端基團， P'係代表該嵌段共聚物之第一嵌段(嵌段A)之第一聚合物鏈， P''係代表該嵌段共聚物之第二嵌段(嵌段B)之第二聚合物鏈，且 X係將P’之末端重複單元接合至P''之末端重複單元之二價鏈接基團，其中X包含1-24個氟，且X之該等氟中之每一者鏈接至該嵌段共聚物之骨架碳。 在某些實施例中，嵌段共聚物具有結構(1b)：

(1b) 其中 E¹ 係單價第一末端基團， E² 係單價第二末端基團， P'係代表該嵌段共聚物之第一嵌段(嵌段A)之第一聚合物鏈， P''係代表該嵌段共聚物之第二嵌段(嵌段B)之第二聚合物鏈，且 X係將P'之末端重複單元接合至P''之末端重複單元之二價鏈接基團，其中X包含含有1-24個碳之全氟烷烴，且X係在兩個末端直接或藉助由1-6個碳組成之烷烴間隔體鏈接至該嵌段共聚物之骨架碳。 在某些實施例中，E¹ -P'在一起形成嵌段A且E² -P''在一起形成嵌段B。在某些實施例中，E¹ -P'在一起形成嵌段B且E² -P''在一起形成嵌段A。在某些實施例中，E¹ 及E² 各自獨立地選自由以下組成之群：H、羥基、鹵基、烷基、芳基及醯基。在具體實施例中，E¹ 或E² 中之一者係H且E¹ 與E² 中之另一者係醯基。在具體實施例中，E¹ 或E² 中之一者係鹵基且E¹ 與E² 中之另一者係醯基。在具體實施例中，E¹ 或E² 中之一者係Br且E¹ 與E² 中之另一者係醯基。在具體實施例中，E¹ 或E² 中之至少一者係鹵基。在具體實施例中，E¹ 或E² 中之至少一者係Br。在具體實施例中，E¹ 或E² 中之至少一者係醯基。在具體實施例中，E¹ 或E² 中之至少一者係乙醯基。 在某些實施例中，第一嵌段包含苯乙烯與三甲基矽基苯乙烯之共聚物。在某些實施例中，X具有以下結構：

， 其中n'係具有1-12、2-10或2-7之值的整數。 在某些實施例中，X具有以下結構：

， 其中n''係具有1-5、1-4或1-3之值的整數。 在具體實施例中，X可為將嵌段A之末端重複單元共價鏈接至嵌段B之末端重複單元之二價鏈接基團，其中X包含1-24、或2-10或2-7個氟。在具體實施例中，X之該等氟中之每一者鏈接至該嵌段共聚物之骨架碳。含氟之部分a)、Si1-Si8矽氧烷部分b)及具有至少18個碳之烴部分c)之特定實例係其中如下者： a) X係含氟之直鏈烴基團、含氟之具支鏈烴基團、含氟之直鏈烷基醚基團、含氟之具支鏈烷基醚基團及其混合物， b) X係Si₁ -Si₈ 矽氧烷部分、碳矽烷、矽烯及其混合物，且 c) X係具有至少18個碳之直鏈烴基團及具有至少18個碳之具支鏈烴。 在某些態樣中，X係下式(C-1)之氟化伸烷基：

其中 鏈接至氟之每一碳係嵌段共聚物之骨架碳， n'係具有2-12、2-10或2-7之值的整數， m'係具有1-5、1-4或2-3之值的整數，且 k'係具有1-5、1-4或2-3之值的整數。 在某些態樣中，X係式(C-2)之二價直鏈氟化環氧乙烷基團：

(C-2)， 其中 鏈接至氟之每一碳係該嵌段共聚物之骨架碳，且 n''係具有1-5、1-4或2-3之值的整數。 在本發明之一個態樣中，結構(1a)及(1b)中之接合部分X具有小於約30 mN m^-1 之表面能。在更特定實施例中，接合部分具有介於30 mN m^-1 與10 mN m^-1 之間、較佳介於25 mN m^-1 與14 mN m^-1 之間之表面能。 通常，適用於該等發明之結構(1a)及(1b)的嵌段共聚物具有在約3,000 g/mol至約500,000 g/mol範圍內之重量平均分子量(M_w )及約1,000至約60,000之數量平均分子量(M_n )以及約1.01至約6、或1.01至約2或1.01至約1.5之多分散性(M_w /M_n ) (PD)。其他實施例係其中在結構(1a)及(1b)中，a係1或2之整數。另一實施例係其中b為1至2之整數。在具有結構(1a)或(1b)之嵌段共聚物之另一實施例中，M_n 在4,000至150,000之範圍內且多分散性(PD)在1.01至5.0之範圍內，更佳1.01至2.0。 在本發明之另一實施例中，嵌段A或嵌段B中之一者包含相對於其他嵌段對製造IC裝置中通常採用之電漿蝕刻技術具有抗性之重複單元；且其他嵌段在該等相同電漿蝕刻條件下迅速蝕刻或可藉由化學或光化學製法去除。當該等材料用溶劑進行調配且塗佈於圖案化基板上時，此性質使得自組裝結構域圖案之圖案能夠轉移至基板中。若自組裝在圖案化基板上進行，則其係引導式自組裝。新穎嵌段共聚物之引導式自組裝之製法可(例如)使用製圖磊晶方法或化學磊晶方法進行。 本發明之另一實施例係其中結構(1a)或(1b)中之嵌段A包含衍生自烯系不飽和可聚合單體之單元或衍生自環狀單體之開環聚合(ROP)之單元，且其中嵌段B包含衍生自烯系不飽和可聚合單體之單元或衍生自環狀單體之開環聚合(ROP)之單元，且進一步其中聚合嵌段A及B彼此不同且係相可分離的。 本發明之另一態樣係其中嵌段A或B係衍生自乙烯基可聚合單體。在其他實施例中，嵌段A及嵌段B中之每一者獨立地衍生自乙烯基芳基單體、內酯、內醯胺、環氧化物、環狀碳酸酯單體或烯系不飽和可聚合單體。在具體實施例中，嵌段A及嵌段B化學上不同且係相可分離的(例如，形成相偏析之交替結構域之圖案)。 在某些實施例中，嵌段A包含式(A-1)之烯系重複單元：

(A-1)， 其中 i) 每一R^w 係選自由以下組成之群之單價基團：H、F、甲基、乙基及三氟甲基(*-CF3)，且 ii) 每一R^d 係包含鏈接至碳1之芳香族環之單價基團。 在某些實施例中，嵌段A包含選自由以下組成之群之烯系重複單元

及其組合。 在某些實施例中，嵌段B包含脂肪族碳酸酯重複單元。在某些實施例中，脂肪族碳酸酯重複單元包含懸掛酯基團。在具體實施例中，脂肪族碳酸酯重複單元具有式(B-4)之結構：

(B-4)， 其中R^g 係包含1-20、1-10或2-5個碳之單價烴基。 在某些實施例中，R^g 係選自由以下組成之群：甲基、乙基、丙基、丁基、戊基、己基及苄基。在具體實施例中，R^g 係甲基。 在某些實施例中，嵌段B包含脂肪族酯重複單元。在某些實施例中，脂肪族酯重複單元具有結構

其中j'係具有0-4、0-3或1-2之值的整數。 在某些實施例中，脂肪族酯重複單元具有結構

。 在某些實施例中，嵌段B包含脂肪族醚重複單元。在具體實施例中，脂肪族醚重複單元係選自由以下組成之群：環氧乙烷、環氧丙烷、開環縮水甘油醚及其組合。 在某些實施例中，嵌段B係包含選自由以下組成之群之重複單元的均聚物

結構(1a)或(1b)之另一實施例係其中結構(1a)或(1b)中之鏈接基團X係具有3至7個選自多價雜原子、包含雜原子之多價基團、多價有機基團、含有雜原子之多價有機基團及其組合之附接點之部分。X部分之更特定實例係C₁ -C₃₀ 直鏈伸烷基氧基部分、C₃ -C₃₀ 具支鏈伸烷基氧基部分、C₁ -C₂₀ 胺基甲酸酯-直鏈伸烷基部分(-N(R₁₁ )-C(=O)-O-直鏈伸烷基)、C₃ -C₃₀ 胺基甲酸酯-具支鏈伸烷基部分(-N(R₁₁ )-C(=O)-O-具支鏈伸烷基部分)、C₁ -C₂₀ 脲-直鏈伸烷基部分(-N(R₁₁ )-C(=O)-N(R₁₁ )-直鏈伸烷基)、C₃ -C₃₀ 脲-具支鏈伸烷基部分(-N(R₁₁ )-C(=O)-N(R₁₁ )-具支鏈伸烷基部分)、C₁ -C₂₀ 硫脲-直鏈伸烷基部分(-N(R₁₁ )-C(=S)-N(R₁₁ )-直鏈伸烷基)、C₃ -C₃₀ 硫脲-具支鏈伸烷基部分(-N(R₁₁ )-C(=S)-N(R₁₁ )--具支鏈伸烷基部分)，其中R₁₁ 係氫或C₁ 至C₄ 烷基；1,2,3-三唑部分、1,2,3-三唑C₁ -C₃₀ 伸烷基部分、1,2,3-三唑C₃ -C₃₀ 具支鏈伸烷基部分、1,2,3-三唑C₃ -C₃₀ 環狀伸烷基部分、1,2,3-三唑C₁ -C₃₀ 伸烷基氧基部分、1,2,3-三唑C₃ -C₃₀ 具支鏈伸烷基氧基部分、1,2,3-三唑C₃ -C₃₀ 環狀伸烷基氧基部分、C₃ -C₃₀ 環烷氧基部分、C₃ -C₃₀ 直鏈伸烷基氧基羰基部分、C₅ -C₃₀ 具支鏈伸烷基氧基羰基部分、C₃ -C₃₀ 環烷氧基羰基部分、C₁ -C₃₀ 直鏈氟伸烷基部分、C₃ -C₃₀ 具支鏈氟伸烷基部分、C₆ -C₃₀ 環狀氟伸烷基部分、C₆ -C₃₀ 伸芳基部分、C₆ -C₃₀ 氟伸芳基部分、C₅ -C₃₀ 氧基伸烷基氧基羰基伸烷基部分、C₂ -C₃₀ 伸烷基氧基伸烷基部分、芳基經取代之C₈ -C₄₂ 伸烷基氧基部分、芳基經取代之C₈ -C₄₂ 伸烷基氧基伸烷基部分、C₈ -C₄₂ 芳基經取代之伸烷基部分、C₇ -C₃₀ 伸烷基伸芳基部分、C₇ -C₃₀ 氟伸烷基伸芳基部分及其組合。 此態樣之更特定實施例係當X部分選自C₅ -C₃₀ 氧基伸烷基氧基羰基伸烷基部分、C₂ -C₃₀ 伸烷基氧基伸烷基部分、芳基經取代之C₈ -C₄₂ 伸烷基氧基部分、芳基經取代之C₈ -C₄₂ 伸烷基氧基伸烷基部分或C₈ -C₄₂ 芳基經取代之伸烷基部分時。 結構(1a)或(1b)之其他實施例係其中部分X係含氟烴基團，例如直鏈C₁ -C₁₀ 氟伸烷基、C₃ -C₁₀ 具支鏈氟伸烷基、伸烷基氟伸烷基(-(CH₂ )_q (CF₂ )_r -CF₂ -)、含CFH之伸烷基氟伸烷基(-(-CH_2- )_q (CHF)_q2 (CF₂ )_r -CF₂ -)、伸烷基氟醚-氟伸烷基-(-CH_2- )_q (-CF₂ -O-)_s (-CF₂ CF₂ -O-)_t (CF₂ )_u CF₂ -、含CHF之伸烷基氟醚-氟伸烷基(-CH_2- )_q (CHF)_q2 (-CF₂ -O-)_s (-CF₂ CF₂ -O-)_t (CF₂ )_u CF₂ -或具有結構(2)之部分

(2) 其中q係0至10之整數，q2係1至10之整數，r係1至10之整數，s係0至10之整數，t係1至10之整數，u係介於0與10間之整數，x為1至5，y為1至5，且P係直接鍵、C₁ 至C₄ 伸烷基或-CH₂ -CH₂ -(CF₂ )₄ -部分。 本發明之另一態樣係其中結構(1a)或(1b)具有包含氧基伸烷基氧基羰基伸烷基部分之X部分。在本發明之此態樣中，新穎嵌段共聚物可藉由原子-轉移自由基-聚合(ATRP)起始劑或開環聚合(ROP)起始劑製得。 具有結構(1a)或(1b)及上述亞結構之嵌段共聚物可藉由各種方法製得，例如，藉由使用原子-轉移自由基-聚合(ATRP)及開環聚合(ROP)起始劑來製備嵌段共聚物，在陰離子嵌段聚合中使用1,1-二苯乙烯(DPE)衍生物作為起始劑及封端劑來製備嵌段共聚物。 方案1顯示包含氧基-X-羰基伸烷基部分之ATRP及ROP起始劑之合成。可採用此起始劑以製得結構(1a)或(1b)之新穎嵌段共聚物。類似地，其他類型之X部分可藉由使用含有適宜X部分之適宜醇附接至該等起始劑，該等X部分係例如含氟之直鏈烴基團、含氟之具支鏈烴基團、含氟之直鏈伸烷基醚基團、含氟具支鏈伸烷基醚基團或其混合物、Si₁ -Si₈ 矽氧烷部分、碳矽烷、矽烯或具有多於18個碳之直鏈烴鏈。

方案 1 具有接合組態X (例如，直鏈全氟烷烴及直鏈全氟醚)之線性接合A-B二嵌段共聚物之合成的非限制性實例顯示於方案2中。如所示，嵌段A係苯乙烯，但可使用其他聚合物嵌段(例如經取代聚苯乙烯)。同樣地，如所示，嵌段B係碳酸三甲酯(TMC)，但可使用其他聚合物嵌段(例如，聚乳酸交酯(PLA)、聚己內酯(PCL)及碳酸三甲酯)。

方案2 可使用二醇以將一個羥基選擇性轉化成原子轉移自由基聚合起始劑。此可經由使二醇與2-溴-2-甲基丙醯溴在三乙胺之存在下在二氯甲烷中反應來實施。單官能化之選擇性可經由緩慢添加2-溴-2-甲基丙醯溴來控制。副產物(例如二官能及未反應試劑)可藉由管柱層析技術去除。單官能試劑將用於在ATRP條件下在與文獻中廣泛使用之配體(參見例如2015年2月20申請之美國專利申請案第14/628,002號，其整體內容以引用的方式併入本文中)複合之CuBr之存在下起始苯乙烯單體。所得具有羥基端基之聚苯乙烯(PS(F)-OH)將用於使用選自環狀碳酸酯、D,L-乳酸交酯、內酯等之環狀單體的開環陰離子配位聚合來合成第二嵌段。使用含羥基之起始劑聚合該等單體所用之條件已在文獻中熟知。在文獻中所述之條件下使用大分子起始劑PS(F)-OH將產生具有期望接合鏈接體X部分之期望二嵌段共聚物。藉由具有結構(1a)或(1b)之新穎嵌段共聚物之開環聚合形成含有衍生自環狀單體之單元的聚合物嵌段可使用針對其中嵌段中之一者已藉由開環聚合衍生之其他類型二嵌段共聚物所闡述之技術(例如揭示於US專利第8,642,086號中者，其整體內容以引用方式併入本文中)來實現。 應瞭解，可採用此項技術中已知之其他偶合反應以藉助結構(1a)或(1b)之鏈接X部分將兩個不同聚合物嵌段接合在一起。 在結構(1a)或(1b)之嵌段共聚物中，嵌段A可為包含衍生自烷基乙烯基單體、甲基丙烯酸烷基酯單體、丙烯酸烷基酯單體、內酯單體、環氧化物單體、內醯胺單體、環狀碳酸酯單體之單元之部分，且嵌段B可為包含衍生自乙烯基芳基單體之重複單元之部分且進一步其中嵌段A及B係相可分離的。 此外，在本發明之另一實施例中，嵌段A可包含衍生自為乙烯基芳基單體之烯系不飽和可聚合單體之單元，且嵌段B可包含衍生自選自丙烯酸酯或甲基丙烯酸酯之烯系不飽和可聚合單體之單元，或包含衍生自選自內酯或環狀碳酸酯之環狀單體之開環聚合(ROP)之單元，且進一步其中嵌段A及B係相可分離的。 在另一實施例中，結構(1a)或(1b)之嵌段共聚物具有一個衍生自開環可聚合單體之嵌段。在另一實施例中，嵌段A及B可衍生自兩種不同烯系不飽和可聚合單體，其中嵌段A及B係相可分離部分。 當具有結構(1a)或(1b)之新穎嵌段共聚物中之聚合物嵌段衍生自環狀羰基單體或烯系不飽和可聚合單體時，該聚合物嵌段可為均聚物或無規共聚物。環狀羰基單體可為立體特異性或非立體特異性的。 藉由具有結構(1a)或(1b)之新穎嵌段共聚物之開環聚合形成含有衍生自環狀單體之單元的聚合物嵌段可使用針對其中嵌段中之一者已藉由開環聚合衍生之其他類型二嵌段共聚物所闡述之技術(例如揭示於以整體引用方式併入本文中之(US 8642086 B2)中者)來實現。 通常，在結構(1a)或(1b)中，二嵌段共聚物中之一個嵌段抗電漿蝕刻，而另一嵌段在相同條件下極迅速地蝕刻，此容許藉由塗佈結構(1a)或(1b)之新穎聚合物並使其退火形成之自組裝圖案圖案轉移至基板中。此自組裝係使用製圖磊晶或化學磊晶方法於圖案化基板上引導。 可採用以形成具有結構(1a)或(1b)之新穎嵌段聚合物中之聚合物嵌段中之烯系不飽和單體可包含衍生自乙烯基芳基、烷基乙烯基單體、甲基丙烯酸烷基酯單體或丙烯酸烷基酯單體之單元。衍生自不飽和單體之具有結構(1a)或(1b)的新穎嵌段共聚物中之聚合物嵌段可為均聚物或無規共聚物。烯系不飽和可為立體特異性或非立體特異性的。 可用於製作本發明新穎嵌段共聚物之嵌段的烷基乙烯基化合物、丙烯酸烷基酯或甲基丙烯酸烷基酯之非限制性實例係其中烷基係以下者：C₁ -C₄ 氟烷基、C₁ -C₁₀ 直鏈烷基部分、C₁ -C₄ 羥基氟伸烷基、C₂ -C₁₀ -烷基氧基伸烷基、C₁ -C₁₀ -羥基伸烷基、C₃ -C₂₀ 具支鏈烷基、C₃ -C₂₀ 環狀烷基、C₂ -C₂₀ 羧基伸烷基、C₃ -C₂₀ 烷基氧基羧基伸烷基或C₃ -C₂₀ 烷基氧基羧基氧基伸烷基；不含有耐火元素之其他取代基亦可能。該等實例中附接至羧基部分之烷基亦可為在與藉由熱酸生成劑或光酸生成劑形成之強酸反應時能夠釋放游離羧基部分之酸可裂解基團(例如三級酯、縮醛或縮酮)。若欲使用衍生自烷基乙烯基化合物、丙烯酸烷基酯或甲基丙烯酸烷基酯之嵌段作為抗蝕刻嵌段部分，則烷基可經含有耐火元素之部分取代，例如C₃ -C₂₀ 三烷基矽基、C₃ -C₂₀ 三烷基鍺基、C₃ -C₂₀ 三烷基錫基或C₃ -C₂₀ 三烷基鈦基。 可用於製作本發明結構(1a)或(1b)之新穎嵌段共聚物之抗蝕刻嵌段之乙烯基芳基化合物的非限制性實例係未經取代之苯乙烯、未經取代之乙烯基萘、未經取代之乙烯基蒽、未經取代之乙烯基芘及諸如此類；或含有一或多個以下取代基之該等芳基部分：例如C₁ -C₂₀ 烷基、C₁ -C₂₀ 羥基烷基、C₂ -C₁₀ -烷基氧基伸烷基、C₁ -C₄ 氟烷基、C₁ -C₄ 羥基氟伸烷基、羥基、經酸不穩定基團封端之羥基、羧基、經酸不穩定基團封端之羧基(該等酸可裂解部分當與膜中所存在藉由熱酸生成劑或光酸生成劑形成之強酸反應時能夠釋放游離羥基或游離羧基部分)、氟醇基團、C₃ -C₂₀ 三烷基矽基、C₃ -C₂₀ 三烷基鍺基、C₃ -C₂₀ 三烷基錫基、C₃ -C₂₀ 三烷基鈦基、C₂ -C₂₀ 烷基羰基、C₂ -C₂₀ 烷基羰基氧基、C₁ -C₂₀ 烷氧基或C₉ -C₃₆ 參(三烷基矽基)矽基；未經取代之乙烯基萘及經以下取代之乙烯基萘：C₁ -C₂₀ 烷基、C₃ -C₂₀ 三烷基矽基、C₃ -C₂₀ 三烷基鍺基、C₃ -C₂₀ 三烷基錫基、C₃ -C₂₀ 三烷基鈦基、C₂ -C₂₀ 烷基羰基、C₂ -C₂₀ 烷基羰基氧基、C₁ -C₂₀ 烷氧基、C₉ -C₃₆ 參(三烷基矽基)矽基；乙烯基蒽；經以下取代之乙烯基蒽：C₁ -C₂₀ 烷基、C₃ -C₂₀ 三烷基矽基、C₃ -C₂₀ 三烷基鍺基、C₃ -C₂₀ 三烷基錫基、C₃ -C₂₀ 三烷基鈦基、C₂ -C₂₀ 烷基羰基、C₂ -C₂₀ 烷基羰基氧基、C₁ -C₂₀ 烷氧基、C₉ -C₃₆ 參(三烷基矽基)矽基；乙烯基芘；經以下取代之乙烯基芘：C₁ -C₂₀ 烷基、C₃ -C₂₀ 三烷基矽基、C₃ -C₂₀ 三烷基鍺基、C₃ -C₂₀ 三烷基錫基、C₃ -C₂₀ 三烷基鈦基、C₂ -C₂₀ 烷基羰基、C₂ -C₂₀ 烷基羰基氧基、C₁ -C₂₀ 烷氧基或C₉ -C₃₆ 參(三烷基矽基)矽基或諸如此類。 在具有結構(1a)或(1b)之新穎二嵌段聚合物之一個實施例中，兩個聚合物嵌段衍生自兩種不同的烯系不飽和單體，一個嵌段係抗電漿蝕刻的且衍生自乙烯基芳基化合物、乙烯基烷基、甲基丙烯酸烷基酯或丙烯酸烷基酯，其中烷基含有如上所述之耐火元素，而另一嵌段利用相同電漿化學迅速蝕刻，例如衍生自烷基乙烯基、丙烯酸烷基酯、甲基丙烯酸烷基酯之嵌段，其中烷基部分不含耐火元素。 在具有結構(1a)或(1b)之新穎二嵌段聚合物之另一實施例中，一個聚合物嵌段係抗蝕刻的且衍生自乙烯基芳基化合物、乙烯基烷基、甲基丙烯酸烷基酯或丙烯酸烷基酯，其中烷基含有如上所述之耐火元素，而利用相同電漿化學迅速蝕刻之另一嵌段衍生自環狀單體(例如環氧化物、內酯、內醯胺或環狀碳酸酯)之開環聚合。該等環狀單體可含有一或多個不含耐火元素之取代基或芳香族環。可能取代基之非限制性實例係羥基、C₁ -C₂₀ 烷基、C₁ -C₂₀ 羥基烷基、C₂ -C₁₀ -烷基氧基伸烷基、鹵基(F、Cl、Br、I)、鹵烷基、氰基、C₁ -C₄ 氟烷基、C₁ -C₄ 羥氟伸烷基、羥基、經酸不穩定基團封端之羥基、羧基、經酸不穩定基團封端之羧基、羧基伸烷基、羧基由酸不穩定基團封端之羧基伸烷基、烷基氧基羰基、烷基羰基、含有雙碳鍵或三碳鍵之烷基及不含耐火元素之其他取代基。 可用作結構(1a)或(1b)之新穎嵌段共聚物中之嵌段中之一者的前體之內酯的特定實例係如下：β-丙內酯、γ-丁內酯、δ-戊內酯、ε-己內酯、β-丁內酯、γ-戊內酯、新戊內酯、1,5-二氧雜環庚-2-酮、5-(苄基氧基)氧雜環庚-2-酮；環狀碳酸酯，選自碳酸三亞甲基酯、碳酸四亞甲基酯、碳酸五亞甲基酯；醣苷、2-溴-2-甲基丙酸7-側氧基氧雜環庚-4-基酯、5-苯基氧雜環庚-2-酮、5-甲基氧雜環庚-2-酮、1,4,8-三氧雜(4,6)螺-9-十一烷、5-(苄基氧基甲基)氧雜環庚-2-酮、3-羥基-2-(羥基甲基)-2-甲基丙酸7-側氧基氧雜環庚-4-基酯、(Z)-6,7-二氫氧雜環庚三烯-2(3H)-酮、D-乳酸交酯、L-乳酸交酯、內消旋-乳酸交酯或含有諸如以下其他取代基之該等材料：羥基、C₁ -C₂₀ 烷基、C₁ -C₂₀ 羥基烷基、C₂ -C₁₀ -烷基氧基伸烷基、鹵基(F、Cl、Br、I)、鹵烷基、氰基、C₁ -C₄ 氟烷基、C₁ -C₄ 羥基氟伸烷基、羥基、經酸不穩定基團封端之羥基、羧基、經酸不穩定基團封端之羧基、羧基伸烷基、羧基經酸不穩定基團封端之羧基伸烷基、烷基氧基羰基、烷基羰基、含有雙碳或三碳鍵結耐火元素之烷基，例如C₃ -C₂₀ 三烷基矽基、C₃ -C₂₀ 三烷基鍺基、C₃ -C₂₀ 三烷基錫基或C₃ -C₂₀ 三烷基鈦基。 可用作結構(1a)或(1b)之新穎嵌段共聚物中之嵌段中之一者的前體之碳酸酯的特定實例係如下：碳酸三亞甲基酯、碳酸四亞甲基酯、碳酸五亞甲基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸甲基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸第三丁基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸乙酯、5-甲基-2-側氧基-1,3-二噁烷-5-羰基氯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸苄基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸2-(四氫-2H-吡喃-2-基氧基)乙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸2,2,3,3,4,4,5,5,6,6,7,7,7-十三氟庚基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸2,2,2-三氟乙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸丙-2-炔基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸烯丙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸2-(2-甲氧基乙氧基)乙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸3-(第三丁基硫基)丙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸2-(第三丁氧基羰基胺基)乙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸2-(吡啶-2-基二氫硫基)乙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸4-(羥基甲基)苄基酯、4-(5-甲基-2-側氧基-1,3-二噁烷-5-羰基氧基)六氫吡啶-1-甲酸第三丁基酯、N-苄基-5-甲基-2-側氧基-1,3-二噁烷-5-甲醯胺、N-異丙基-N,5-二甲基-2-側氧基-1,3-二噁烷-5-甲醯胺、5,5-二甲基碳酸三亞甲基酯(5,5-二甲基-1,3-二噁烷-2-酮)、5-甲基碳酸三亞甲基酯(5-甲基-1,3-二噁烷-2-酮)、5,5-二乙基碳酸三亞甲基酯(5,5-二乙基-1,3-二噁烷-2-酮)、及5-乙基碳酸三亞甲基酯(5-乙基-1,3-二噁烷-2-酮)或含有諸如以下其他取代基之該等材料中之任一者：羥基、C₁ -C₂₀ 烷基、C₁ -C₂₀ 羥基烷基、C₂ -C₁₀ -烷基氧基伸烷基、鹵基(F、Cl、Br、I)、鹵烷基、氰基、C₁ -C₄ 氟烷基、C₁ -C₄ 羥基氟伸烷基、羥基、經酸不穩定基團封端之羥基、羧基、經酸不穩定基團封端之羧基、羧基伸烷基、羧基經酸不穩定基團封端之羧基伸烷基、烷基氧基羰基、烷基羰基、含有雙碳或三碳鍵結耐火元素之烷基，例如C₃ -C₂₀ 三烷基矽基、C₃ -C₂₀ 三烷基鍺基、C₃ -C₂₀ 三烷基錫基或C₃ -C₂₀ 三烷基鈦基。 可用作結構(1a)或(1b)之新穎嵌段共聚物中之嵌段中之一者的前體之環氧化物之特定實例係如下：環氧丙烷、環氧丁烷、環氧乙烷、苯乙烯氧化物、具有為C₁ -C₂₀ 烴(直鏈、脂肪族、芳香族、具支鏈等)之R基團之縮水甘油醚、及含矽之環氧單體(例如具有附接至氧或碳之三甲基矽基(TMS)懸掛基團)或具有諸如以下其他取代基之該等材料中之任一者：羥基、C₁ -C₂₀ 烷基、C₁ -C₂₀ 羥基烷基、C₂ -C₁₀ -烷基氧基伸烷基、鹵基(F、Cl、Br、I)、鹵烷基、氰基、C₁ -C₄ 氟烷基、C₁ -C₄ 羥基氟伸烷基、羥基、經酸不穩定基團封端之羥基、羧基、經酸不穩定基團封端之羧基、羧基伸烷基、羧基經酸不穩定基團封端之羧基伸烷基、烷基氧基羰基、烷基羰基、含有雙碳或三碳鍵結耐火元素之烷基，例如C₃ -C₂₀ 三烷基矽基、C₃ -C₂₀ 三烷基鍺基、C₃ -C₂₀ 三烷基錫基或C₃ -C₂₀ 三烷基鈦基。 可用作結構(1a)或(1b)之新穎嵌段共聚物中之嵌段中之一者的前體之內醯胺的特定實例：β-丙內醯胺、γ-丁內醯胺、δ-戊內醯胺、及ε-己內醯胺及具有諸如以下其他取代基之該等內醯胺或該等材料中之任一者：羥基、C₁ -C₂₀ 烷基、C₁ -C₂₀ 羥基烷基、C₂ -C₁₀ -烷基氧基伸烷基、鹵基(F、Cl、Br、I)、鹵烷基、氰基、C₁ -C₄ 氟烷基、C₁ -C₄ 羥基氟伸烷基、羥基、經酸不穩定基團封端之羥基、羧基、經酸不穩定基團封端之羧基、羧基伸烷基、羧基經酸不穩定基團封端之羧基伸烷基、烷基氧基羰基、烷基羰基、含有雙碳或三碳鍵結耐火元素之烷基，例如C₃ -C₂₀ 三烷基矽基、C₃ -C₂₀ 三烷基鍺基、C₃ -C₂₀ 三烷基錫基或C₃ -C₂₀ 三烷基鈦基。 在具有結構(1a)或(1b)之新穎二嵌段聚合物之另一實施例中，一個聚合物嵌段抗蝕刻且衍生自乙烯基芳基化合物或抗蝕刻乙烯基烷基、抗蝕刻甲基丙烯酸烷基酯、抗蝕刻丙烯酸烷基酯或抗蝕刻經取代之環狀單體。乙烯基烷基、甲基丙烯酸烷基酯、丙烯酸烷基酯或經取代之環狀單體之蝕刻抗性係藉由使烷基或環狀單體上之取代基含有如上所述之耐火元素或含有芳基取代基、芳基伸烷基、或烷基伸芳基或多環烷基取代基來賦予。 在具有結構(1a)或(1b)之新穎嵌段共聚物之另一實施例中，可用於形成聚合物嵌段A之烯系不飽和單體可包含衍生自乙烯基芳基單體之單元且聚合物嵌段B可包含衍生自烯系不飽和可聚合單體、內酯或環狀碳酸酯之單元且進一步其中嵌段A及B係相可分離的。在此實施例中，烯系不飽和可聚合單體可選自丙烯酸酯或甲基丙烯酸酯，或包含衍生自選自內酯或環狀碳酸酯之環狀單體之開環聚合(ROP)之單元，其中乙烯基芳基選自由以下組成之群：苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-正丙基苯乙烯、4-異丙基苯乙烯、4-正丁基苯乙烯、4-三甲基矽基苯乙烯、4-環己基苯乙烯、4-環戊基苯乙烯、3-三甲基矽基苯乙烯、4-第三丁基苯乙烯、4-異戊基苯乙烯、4-甲氧基苯乙烯、4-正丙基氧基苯乙烯、4-異丙基氧基苯乙烯、4-正丁基氧基苯乙烯、4-環己基氧基苯乙烯、4-環戊基氧基苯乙烯、4-三甲基矽基氧基苯乙烯、3-三甲基氧基矽基苯乙烯、4-第三丁基氧基苯乙烯、4-異戊基氧基苯乙烯、4-三氟甲基苯乙烯、3-三氟甲基苯乙烯、4-三氟甲基氧基苯乙烯、3-三氟甲基氧基苯乙烯、4-第三丁基氧基羰基氧基苯乙烯、4-第三丁基氧基羰基苯乙烯、4-第三丁氧基羰基氧基苯乙烯、4-乙烯基苯甲酸、4-乙烯基苄醇、4-乙烯基苯甲酸甲基酯、α-甲基苯乙烯、2,4-二甲基苯乙烯、2,5-二甲基苯乙烯，且2,4,6-三甲基苯乙烯，且其中甲基丙烯酸酯若存在，可選自由以下組成之群：甲基丙烯酸甲基酯、甲基丙烯酸乙基酯、甲基丙烯酸丙基酯、甲基丙烯酸正丁基酯、甲基丙烯酸異丙基酯、甲基丙烯酸第三丁基酯、甲基丙烯酸環己基酯、甲基丙烯酸環戊基酯、甲基丙烯酸異莰基酯、甲基丙烯酸3-羥基-1-金剛烷基酯、甲基丙烯酸2-乙基-2-金剛烷基酯、甲基丙烯酸2-金剛烷基酯、甲基丙烯酸乙基環戊基酯、甲基丙烯酸2-乙基-金剛烷基氧基甲基酯、甲基丙烯酸三環[5,2,1,0^2,6 ]癸-8-基酯、甲基丙烯酸2-側氧基金剛烷基酯、甲基丙烯酸2-乙基-2-金剛烷基酯、甲基丙烯酸2-羧基乙基酯甲基酯、甲基丙烯酸2-羧基乙基酯乙基酯、甲基丙烯酸2-羧基乙基酯丙基酯、甲基丙烯酸2-羧基乙基酯正丁基酯、甲基丙烯酸2-羧基乙基酯第三丁基酯、甲基丙烯酸2-羧基乙基酯金剛烷基酯及甲基丙烯酸2-羥基乙基酯，且丙烯酸酯若存在，可選自由以下組成之群：丙烯酸甲基酯、丙烯酸乙基酯、丙烯酸丙基酯、丙烯酸正丁基酯、丙烯酸第三丁基酯、丙烯酸異丙基酯、丙烯酸環己基酯、丙烯酸環戊基酯、丙烯酸異莰基酯、丙烯酸3-羥基-1-金剛烷基酯、丙烯酸2-乙基-2-金剛烷基酯、丙烯酸2-金剛烷基酯、丙烯酸乙基環戊基酯、丙烯酸2-乙基-金剛烷基氧基甲基酯、丙烯酸三環[5,2,1,0^2,6 ]癸-8-基酯、丙烯酸2-側氧基金剛烷基酯、丙烯酸2-乙基-2-金剛烷基酯、丙烯酸2-羧基乙基酯甲基酯、丙烯酸2-羧基乙基酯乙基酯、丙烯酸2-羧基乙基酯丙基酯、丙烯酸2-羧基乙基酯正丁基酯、丙烯酸2-羧基乙基酯第三丁基酯、丙烯酸2-羧基乙基酯金剛烷基酯及丙烯酸2-羥基乙基酯。亦在此實施例中，內酯可選自由以下組成之群：β-丙內酯、γ-丁內酯、δ-戊內酯、ε-己內酯、β-丁內酯、γ-戊內酯、新戊內酯、1,5-二氧雜環庚-2-酮、5-(苄基氧基)氧雜環庚-2-酮、2-溴-2-甲基丙酸7-側氧基氧雜環庚-4-基酯、5-苯基氧雜環庚-2-酮、5-甲基氧雜環庚-2-酮、1,4,8-三氧雜(4,6)螺-9-十一烷、5-(苄基氧基甲基)氧雜環庚-2-酮、3-羥基-2-(羥基甲基)-2-甲基丙酸7-側氧基氧雜環庚-4-基酯、(Z)-6,7-二氫氧雜環庚三烯-2(3H)-酮、乙交酯、D-乳酸交酯、L-外消旋乳酸交酯、1:1 D:L形式乳酸交酯及內消旋-乳酸交酯。亦在此實施例中，環狀碳酸酯可選自由以下組成之群：碳酸三亞甲基酯、碳酸四亞甲基酯、碳酸五亞甲基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸甲基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸第三丁基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸乙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-羰基氯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸苄基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸2-(四氫-2H-吡喃-2-基氧基)乙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸2,2,3,3,4,4,5,5,6,6,7,7,7-十三氟庚基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸2,2,2-三氟乙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸丙-2-炔基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸烯丙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸2-(2-甲氧基乙氧基)乙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸3-(第三丁基硫基)丙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸2-(第三丁氧基羰基胺基)乙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸2-(吡啶-2-基二氫硫基)乙基酯、5-甲基-2-側氧基-1,3-二噁烷-5-甲酸4-(羥基甲基)苄基酯、4-(5-甲基-2-側氧基-1,3-二噁烷-5-羰基氧基)六氫吡啶-1-甲酸第三丁基酯、N-苄基-5-甲基-2-側氧基-1,3-二噁烷-5-甲醯胺、N-異丙基-N,5-二甲基-2-側氧基-1,3-二噁烷-5-甲醯胺、5,5-二甲基碳酸三亞甲基酯(5,5-二甲基-1,3-二噁烷-2-酮)、5-甲基碳酸三亞甲基酯(5-甲基-1,3-二噁烷-2-酮)、5,5-二乙基碳酸三亞甲基酯(5,5-二乙基-1,3-二噁烷-2-酮)及5-乙基碳酸三亞甲基酯(5-乙基-1,3-二噁烷-2-酮)。 在具有結構(1a)或(1b)之新穎嵌段共聚物之另一更特定實施例中，可用於形成聚合物嵌段A之烯系不飽和單體可包含衍生自乙烯基芳基單體之單元且嵌段B可包含衍生自烯系不飽和可聚合單體或內酯之單元，且進一步其中嵌段A及B係相可分離的。在此實施例中，烯系不飽和可聚合單體係選自丙烯酸酯或甲基丙烯酸酯，或包含衍生自環狀碳酸酯之開環聚合(ROP)之單元，其中乙烯基芳基係選自由以下組成之群：苯乙烯、4-甲基苯乙烯及4-乙基苯乙烯，且其中甲基丙烯酸酯若存在，則選自由以下組成之群：甲基丙烯酸甲基酯、甲基丙烯酸乙基酯及甲基丙烯酸丙基酯；且內酯選自由以下組成之群：β-丙內酯、γ-丁內酯,δ-戊內酯、ε-己內酯、β-丁內酯、γ-戊內酯、新戊內酯、1,5-二氧雜環庚-2-酮、5-(苄基氧基)氧雜環庚-2-酮；選自碳酸三亞甲基酯、碳酸四亞甲基酯、碳酸五亞甲基酯之環狀碳酸酯；醣苷、7-側氧基氧雜環庚-4-基2-溴-2-甲基丙酸酯、5-苯基氧雜環庚-2-酮、5-甲基氧雜環庚-2-酮、1,4,8-三氧雜(4,6)螺-9-十一烷、5-(苄基氧基甲基)氧雜環庚-2-酮、7-側氧基氧雜環庚-4-基3-羥基-2-(羥基甲基)-2-甲基丙酸酯、(Z)-6,7-二氫氧雜環庚三烯-2(3H)-酮、D-乳酸交酯、L-乳酸交酯、內消旋-乳酸交酯，且進一步其中嵌段A及B係相可分離的。 本發明亦係關於包含結構(1a)或(1b)之新穎嵌段共聚物及溶劑之組合物。適於單獨或與其他組份組合溶解結構(1a)或(1b)之新穎嵌段共聚物之溶劑包括丙二醇單甲基醚乙酸酯(PGMEA)、丙酸乙氧基乙酯、茴香醚、乳酸乙酯、2-庚酮、環己酮、乙酸戊酯、乙酸正丁酯、正戊基酮(MAK)、γ-丁內酯(GBL)、甲苯及諸如此類。在實施例中，尤其有用之澆注溶劑包括丙二醇單甲基醚乙酸酯(PGMEA)、γ-丁內酯(GBL)或該等溶劑之組合。具有結構(1a)或(1b)之新穎嵌段共聚物在溶劑中之wt%可在0.2 wt%至10 wt%之範圍內。在另一實施例中，該範圍可為0.5 wt%至10 wt%。在再一實施例中，該範圍可為0.5 wt%至5 wt%。在再一更特定實施例中，該範圍可為0.8 wt%至1.2 wt%。在具體實施例中，組合物能夠形成包含嵌段共聚物之膜層，其中該膜層能夠自發地及/或在熱處理時自組裝，由此形成包含嵌段共聚物之各別化學上不同嵌段之相偏析之交替結構域之圖案。 含有結構(1a)或(1b)之新穎嵌段共聚物之溶液可進一步包含選自由以下組成之群之其他組份及/或添加劑：含無機物之聚合物；添加劑，包括小分子、含無機物之分子、表面活性劑、光酸生成劑、熱酸生成劑、淬滅劑、硬化劑、交聯劑、鏈延長劑及諸如此類；及包含上述中之至少一者之組合，其中其他組份及/或添加劑中之一或多者與嵌段共聚物共組裝以形成嵌段共聚物組裝。 在本發明之另一態樣中，包含結構(1a)或(1b)之第一嵌段共聚物之新穎組合物可進一步含有結構(1a)或(1b)之第二不同嵌段共聚物。在本發明之此態樣中，與第一嵌段共聚物不同之第二嵌段共聚物可以總固體之5 wt %至50 wt %存在。 在新穎組合物之另一實施例中，組合物包含結構(1a)或(1b)之嵌段共聚物及第二嵌段共聚物，該第二嵌段共聚物不具有接合基團但包含衍生自如上文針對新穎嵌段共聚物所述之烯系不飽和單體或環狀單體之嵌段。含有高抗蝕刻嵌段及高度可蝕刻嵌段之適宜第二二嵌段共聚物之特定實例可為嵌段共聚物聚(苯乙烯-b-甲基丙烯酸甲酯)。通常，適用於該等發明之嵌段共聚物具有在約3,000 g/mol至約500,000 g/mol範圍內之重量平均分子量(M_w )及約1,000至約60,000之數量平均分子量(M_n )以及約1.01至約6、或1.01至約2或1.01至約1.5之多分散性(M_w /M_n ) (PD)。可用作其他組份之不含接合基團之其他二嵌段共聚物之其他特定非限制性實例係聚(苯乙烯-b-甲基丙烯酸甲基酯)、聚(苯乙烯-b-丁二烯)、聚(苯乙烯-b-異戊二烯)、聚(苯乙烯-b-甲基丙烯酸甲基酯)、聚(苯乙烯-b-烯基芳香族化合物)、聚(苯乙烯-b-(乙烯-丙烯))、聚(苯乙烯-b-(甲基)丙烯酸第三丁基酯)、聚(苯乙烯-b-四氫呋喃)、聚(苯乙烯-b-環氧乙烷)、聚(苯乙烯-b-二甲基矽氧烷)、聚(甲基丙烯酸甲基酯-b-二甲基矽氧烷)及聚(甲基甲基丙烯酸酯-b-4-乙烯基吡啶))。所有該等聚合材料皆共同存在至少一個具有抵抗製造IC裝置通常所用電漿蝕刻技術之重複單元之嵌段及至少一個在該等相同條件下迅速蝕刻或可藉由化學或光化學製法去除之嵌段。此容許引導式自組裝聚合物圖案轉移至基板上以影響通孔形成。 在本發明之此態樣中，第二嵌段共聚物可以總固體之1wt%至20 wt%或更優先5wt%至10 wt %存在。 此新穎組合物之另一實施例係其中其進一步包含均聚物作為另一組份。此均聚物可為衍生自上文先前所闡述作為具有結構(1a)或(1b)之新穎嵌段共聚物之嵌段之適宜前體的烯系不飽和單體或環狀單體中之任一者之均聚物。此一均聚物組份可以固體之0.5 wt %至10 wt %或更特定地1 wt %至5 wt %之含量範圍存在於組合物中。 嵌段A中重複單元之新穎嵌段共聚物對嵌段B中重複單元之新穎嵌段共聚物之莫耳比介於1.2至0.8之間且進一步如上文在所有其可能實施例中所闡述。 本發明係關於在包含新穎嵌段共聚物之引導式自組裝之製法中使用新穎組合物形成圖案。可使用包含引導式自組裝新穎嵌段共聚物之步驟之任一製法。 可使用包含新穎嵌段共聚物之組合物藉由諸如旋轉澆注、浸塗、刮刀式塗佈(doctor blading)、噴霧或任何其他已知製法等製法將新穎組合物施加於基板上形成膜。嵌段共聚物之膜可具有1 nm至1000 nm且更具體而言1 nm至130 nm之厚度。具體而言，膜厚度等於或大於25 nm，具體而言厚度在25 nm至125 nm之範圍內。可視情況使膜退火以促進自組裝並去除缺陷。退火製法包括熱退火、熱梯度退火、溶劑蒸氣退火、熱溶劑蒸氣退火及諸如此類。熱退火可在高於嵌段共聚物之玻璃轉變溫度且低於嵌段共聚物之熱分解溫度之溫度下實施。熱退火可在室溫至約300℃之溫度下實施。熱退火可實施約10 sec至約100小時、更具體而言30秒至1小時之時段。 本發明之嵌段共聚物可形成具有各種形態(包括薄片、圓柱體及球體)之自組裝結構域。該等結構域之大小(例如寬度)可為1 nm至100 nm、2 nm至30 nm或更具體而言3 nm至20 nm。本發明進一步係關於採用結構(1a)或(1b)之新穎嵌段共聚物之新穎製法。由結構(1a)或(1b)之新穎嵌段共聚物賦予之意外結果中之一者係當將該等共聚物塗佈於基板上並使其經歷自組裝時，底層無需為非優先的(例如中性)。此係由於對於由結構(1a)或(1b)中表面活性接合基團之存在賦予之新穎嵌段共聚物結構域的垂直對準而言製法寬容度較大(關於底層表面親和力)。由結構(1a)或(1b)之新穎嵌段共聚物賦予之另一意外結果係其為較無新穎表面活性接合基團之類似嵌段共聚物顯著更厚之嵌段共聚物膜提供相對於基板垂直對準之嵌段共聚物結構域。特定而言，25 nm至125 nm之範圍係可能的。 作為此可如何用於圖案轉移中之非限制性實例，當將新穎嵌段共聚物塗佈於底層(即基板)上並進一步處理時，嵌段共聚物形成包含垂直於底層表面定向之圓柱形微結構域之微相分離式結構域。此係由於結構域均不具有任何與底層結合之優先性，且此在嵌段共聚物組裝中進一步提供平行線/空間圖案。如此定向之結構域在其他處理條件下係熱穩定的。因此，在底層上形成新穎嵌段共聚物之塗層並藉由烘烤及/或退火使其自組裝之後，嵌段共聚物之結構域將形成於底層表面上且保持與底層表面垂直。 可在其他結構域存在下選擇性去除結構域中之一者以生成經蝕刻結構域圖案。此選擇性去除可藉由濕式或乾式製法實現。在一個實例中，濕式或電漿蝕刻可與可選UV曝光一起使用。濕式蝕刻可利用乙酸。可使用標準電漿蝕刻製法，例如包含氧之電漿；另外，電漿中可存在氬、一氧化碳、二氧化碳、CF₄ 、CHF₃ 。在熱可分解聚合物嵌段之情形中，可藉由熱烘烤實現選擇性去除。在另一實例中，可在自組裝後選擇性改質嵌段共聚物結構域中之一者以增加其蝕刻抗性。例如，可藉由化學浸潤自溶液或蒸氣引入抗蝕刻金屬或無機物質。結構域或官能基可選擇性地與諸如矽烷或矽基氯化物等反應性化合物反應。或者，可使用原子層沈積之循環(例如，循序浸潤合成)使抗蝕刻材料浸潤至一個結構域中。在改質後，可使用濕式或乾式蝕刻製法去除抗性較小之結構域。 在選擇性去除製法後，所得經蝕刻結構域圖案可進一步圖案轉移至基板層中。使用已知技術將該等自組裝嵌段共聚物圖案轉移至下伏基板中。 在一些情形中，可有利的在轉移至基板中之前或在轉移至基板之層中之後將圖案之影調反轉。此可藉由標準影調反轉製法(例如，利用抗蝕刻旋塗介電影調反轉材料回填有機圖案)來實現。 圖1a及1b分別顯示結構(1a)或(1b)之新穎嵌段共聚物之示意性繪示及其自組裝之示意性繪示。特定而言，圖1a顯示新穎嵌段共聚物之示意性繪示。 圖1b顯示圖1a中示意性繪示之嵌段共聚物在塗佈於正經歷兩種類型自組裝之底層(即基板)上時之示意性繪示。在圖1a之俯視圖中，嵌段共聚物之膜形成定向以形成垂直定向薄片之結構域。在圖1b之仰視圖中，膜中之該等結構域定向以形成垂直定向之圓柱體結構域。 圖2a-c顯示結構(1a)或(1b)之新穎嵌段共聚物之引導式自組裝(DSA)之示意圖。特定而言，圖2a顯示製圖磊晶DSA，其中大多數新穎嵌段共聚物侷限於形貌預圖案中之凹陷區域內，此新穎嵌段共聚物之結構域細分凹陷區域。圖2b顯示在淺的週期形貌預圖案上方及其內之此新穎嵌段共聚物塗層，其中此嵌段共聚物之結構域與形貌預圖案對準。最後，圖2c顯示化學磊晶DSA，其中此新穎嵌段共聚物之膜係塗佈於包含優先及非優先區域(例如中性區域之非限制性實例)之化學預圖案上方，其中新穎嵌段共聚物之結構域與潤濕特徵對準。與習用嵌段聚合物不同，具有表面活性接合基團之結構(1a)或(1b)之本發明材料不需要實質上非優先區域之存在且因此提供相對於底層表面親和力較寬之製法寬容度。亦即，該等新穎材料可針對較廣範圍之底層表面性質在自組裝期間形成垂直於基板定向之結構域。此可使得能夠跨越具有(例如)不完美或非均勻表面性質之表面達成較穩健SA性能。不完美或非均勻表面性質可能係由底層材料之損壞、污染、不完美沈積/接枝條件、雜質、差的組成均勻性或其他原因造成的。 在上述製法及以下採用包含結構(1a)或(1b)之新穎嵌段共聚物之新穎組合物之本發明製法中，可使用其他類型之基板。作為實例，可使用具有高碳底層之塗層及矽抗反射塗層之基板作為基板。高碳底層可具有約20 nm至約2微米之塗層厚度。在此塗層上方塗佈約10 nm至約100 nm之矽抗反射塗層。在期望新穎嵌段共聚物之自組裝圓柱體垂直於基板定向之情況下，可採用中性層。 本發明亦可用於各種其他基板中，例如藉由化學蒸氣沈積(CVD)、物理蒸氣沈積(PVD)及原子層沈積(ALD)製備之彼等。使用該等CVD及PVD製備基板論述於以下參考文獻中：「HANDBOOK OF THIN-FILM DEPOSITION PROCESSES AND TECHNIQUES, Principles, Methods, Equipment and Applications, 第二版, 由Krishna Seshan編輯, Intel Corporation, Santa Clara, California, Copyright © 2002，Noyes Publications, 國會圖書館目錄卡片編號(Library of Congress Catalog Card Number)：2001135178, ISBN: 0-8155-1442-5, Noyes Publications / William Andrew Publishing, 13 Eaton Avenue Norwich, NY 13815, 第1章標題：Deposition Technologies and Applications: Introduction and Overview, 第11頁-第43頁, 第1章，作者：Werner Kern及Klaus K. Schuegraf」。藉由ALD製備基板闡述於以下參考文獻中：「Chemical Review 2010, 110, 第111-131頁」。 在本發明之另一態樣中，包含具有結構(1a)或(1b)之嵌段共聚物之新穎組合物係用於使用具有Lo週期性之嵌段共聚物之層使第一及第二嵌段共聚物結構域在未圖案化基板上方垂直定向之方法中，該方法包含步驟a)及b)；其中， a) 在該未圖案化基板上自新穎組合物形成嵌段共聚物之塗層；及 b) 使該嵌段共聚物之該層退火以產生在該未圖案化基板上垂直定向之非零正整數數量之第一及第二嵌段共聚物結構域。 在此發明性方法中，未圖案化基板可選自由以下組成之群：聚合物刷層、交聯聚合物層、自組裝單層、抗反射塗層之層、藉由化學蒸氣沈積(CVD)沈積之層、碳層、藉由物理蒸氣沈積(PVD)沈積之層、藉由原子層沈積(ALD)沈積之層。 在本發明之另一態樣中，包含具有結構(1a)或(1b)之嵌段共聚物之新穎組合物係用於如下方法中：使用包含具有L_O 週期性之嵌段共聚物之塗層使第一及第二嵌段共聚物結構域在第一圖案化基板(其中基板上圖案形貌之高度為至少0.7倍Lo)上方垂直定向並使結構域與圖案對準，該方法包含步驟a)及b)；其中， a) 在該第一形貌基板上利用包含具有結構(1a)或(1b)之嵌段共聚物之上文所提及之新穎組合物之組合物形成具有接合基團之嵌段共聚物之塗層，其中嵌段共聚物塗層之平均厚度小於第一形貌基板之形貌之高度，其中嵌段共聚物層側向地受形貌限制；及， b) 使嵌段共聚物層退火以產生第一及第二嵌段共聚物結構域，該等結構域垂直定向於該第一圖案化基板且侷限於凹陷區域內。 在本發明之此態樣中，第一圖案化基板係於底層上方之形貌形成材料，其中形貌形成材料可選自由以下組成之群：抗蝕劑材料、交聯聚合物層、抗反射塗層之層、藉由化學蒸氣沈積(CVD)沈積之層、藉由物理蒸氣沈積(PVD)沈積之層、藉由原子層沈積(ALD)沈積之層，且進一步其中底層係選自由以下組成之群：聚合物刷層、交聯聚合物層、自組裝單層、抗反射塗層之層、藉由化學蒸氣沈積(CVD)沈積之層、藉由物理蒸氣沈積(PVD)沈積之層、藉由原子層沈積(ALD)沈積之層。 此外，在本發明之此態樣中，抗蝕劑材料可選自由以下組成之群：i線光阻劑、g線光阻劑、284 nm光阻劑、193 nm光阻劑、遠紫外光阻劑及電子束光阻劑。另一實施例係其中抗反射塗層材料選自由以下組成之群：底部抗反射塗層、矽抗反射塗層及鈦抗反射塗層。 在本發明之另一態樣中，包含具有結構(1a)或(1b)之嵌段共聚物之新穎組合物係用於如下方法中：使用包含嵌段共聚物之新穎塗層，使具有Lo週期性之第一及第二嵌段共聚物結構域在具有形貌高度大於0.7倍Lo及節距P₁ (其中節距P₁ 係非零正整數乘以Lo)之形貌圖案之第二圖案化基板上方垂直定向，並使結構域與圖案對準，該方法包含步驟a)及b)；其中， a) 在該第二圖案化基板上利用上文所提及包含具有結構(1a)或(1b)之嵌段共聚物之新穎組合物之組合物自具有表面活性接合基團之嵌段共聚物形成塗層，其中嵌段共聚物塗層之厚度超過第二圖案化基板之形貌之高度；及， b) 使該嵌段共聚物層退火以產生在該第二圖案化基板上垂直定向之非零正整數數量之第一及第二嵌段共聚物結構域，並使該等結構域與該第二圖案化基板對準，其中垂直定向之結構域之總和等於或大於該形貌圖案之節距P₁ 。 在本發明之此態樣中，第一圖案化基板係藉由利用選擇性修整有機特徵並改質無機層之暴露表面區域之電漿處理無機層頂部上之形貌有機特徵來製備。在此實施例之另一態樣中，在薄底層上方形貌有機特徵之材料係選自由以下組成之群：圖案化i線光阻劑、g線光阻劑、248 nm光阻劑、193 nm光阻劑、遠紫外光阻劑及電子束光阻劑。在此實施例之最後態樣中，底層可為抗反射塗層，或無機層材料係選自矽抗反射塗層或鈦抗反射塗層。 在本發明之另一態樣中，包含具有結構(1a)或(1b)之嵌段共聚物之新穎組合物係用於如下方法中：使用包含其中嵌段共聚物具有Lo週期性之嵌段共聚物之塗層，使第一及第二嵌段共聚物結構域在具有節距P₂ (其中節距P₂ 係非零正整數乘以Lo)之表面化學預圖案之基板上方垂直定向並使結構域與預圖案對準，該方法包含步驟a)及b) a) 在具有表面化學預圖案之基板上利用含有結構(1a)或(1b)之嵌段共聚物之新穎組合物形成具有表面活性接合基團之嵌段共聚物之塗層， b) 使該嵌段共聚物層退火以產生與具有節距P₂ 之表面化學預圖案之基板對準之垂直定向之第一及第二嵌段共聚物結構域。 在本發明之此態樣中，具有表面化學預圖案之基板包含交替之優先潤濕區域及定向控制區域，其中優先潤濕區域之寬度及定向控制區域之寬度之總和等於預圖案節距P₂ ，其中定向控制區域中所用材料支援嵌段共聚物結構域之垂直定向，且優先潤濕區域對嵌段共聚物結構域中之一者具有與另一嵌段共聚物結構域相比低之界面能量。 在另一態樣中，包含具有結構(1a)或(1b)之嵌段共聚物之組合物用於方法中，該方法包含： 提供包含頂部層(底層)之第一分層結構； 形成設置於底層上包含結構(1a)或(1b)之嵌段共聚物之膜層，其中膜層具有與大氣界面接觸之頂部表面；及 使用熱處理使或誘導膜層之嵌段共聚物自組裝，由此形成包含具有特徵節距(Lo)之相偏析結構域圖案之第二分層結構，該結構域圖案包含含有嵌段共聚物之各別化學上不同嵌段之垂直定向交替結構域。 在一個實施例中，結構域圖案包含薄片狀結構域。在另一實施例中，結構域圖案包含圓柱形結構域。在某些實施例中，特徵節距(Lo)為約4 nm至約80 nm、約4 nm至約50 nm或約10 nm至約50 nm。在某些實施例中，底層由其中X之所有氟由氫替代之其他方面相同之自組裝嵌段共聚物之結構域中之一者潤濕。在某些實施例中，大氣界面由其中X之所有氟由氫替代之其他方面相同之自組裝嵌段共聚物之結構域中之一者潤濕。在某些實施例中，方法亦包括選擇性蝕刻該等結構域中之一者，由此形成包含含有自組裝嵌段共聚物之一或多個剩餘結構域之經蝕刻結構域圖案之第三分層結構。在具體實施例中，方法包括將經蝕刻結構域圖案轉移至基板。在具體實施例中，該經蝕刻結構域圖案至基板之該轉移係使用影調反轉製法相對於經蝕刻結構域圖案實施。在某些實施例中，使用熱處理使膜層之嵌段共聚物自組裝之該誘導包含在介於約80℃與約250℃、約100℃與約250℃或約120℃與約200℃之間之溫度下烘烤膜層達約1秒與約24小時、約10秒與約20小時或約1分鐘與約10小時之間。在某些實施例中，該方法包含在組合物之該設置之前形成設置於底層上之形貌抗蝕劑圖案，其中包含用於自組裝之嵌段共聚物之膜層實質上侷限於形貌抗蝕劑圖案之凹陷區域。 在另一態樣中，在方法中採用包含具有結構(1a)或(1b)之嵌段共聚物之組合物，該方法包含： 提供第一多層結構，其包含具有用於引導結構(1a)或(1b)之嵌段共聚物之自組裝之預圖案的頂部表面； 形成設置於預圖案之頂部表面上包含嵌段共聚物之膜層，該膜層包含與大氣界面接觸之頂部表面，且膜層包含與預圖案之頂部表面接觸之底部表面；及 使用熱處理使或誘導嵌段共聚物自組裝，由此形成包含嵌段共聚物之相偏析結構域圖案(結構域圖案)之第二多層結構，該結構域圖案設置於預圖案之頂部表面上。 在某些實施例中，預圖案之頂部表面優先由其中X之所有氟由氫替代之其他方面相同之自組裝嵌段共聚物之結構域中之一者潤濕。在某些實施例中，結構域垂直於第一多層結構之底部層之主平面定向。在某些實施例中，方法包括選擇性移除該等結構域中之一者，由此形成包含經蝕刻結構域圖案之第三多層結構，該經蝕刻結構域圖案包含該結構域圖案之一或多個剩餘結構域。在某些實施例中，方法包括將經蝕刻結構域圖案轉移至第三多層結構之一或多個下伏層。在某些實施例中，經蝕刻結構域圖案之該轉移係使用影調反轉製法實施。在某些實施例中，該預圖案係包含側壁高度大於或等於膜層厚度之形貌特徵之製圖磊晶預圖案，且其中膜層實質上侷限於預圖案之凹陷區域。在某些實施例中，預圖案係包含側壁高度小於膜層厚度之形貌特徵之化學磊晶預圖案，且其中膜層設置於預圖案之最頂部及最底部表面上。 以下特定實例將提供產生及利用本發明組合物之方法之詳細說明。然而，該等實例並不意欲以任何方式限制或約束本發明之範圍，且不應將該等實例理解為提供實踐本發明必須且僅能使用之條件、參數或值。實例 儀器及化學品 表1中未指定之化學品係自Aldrich Chemical Company (Sigma-Aldrich Corp St. Louis, MO, USA)獲得且按原樣使用。除非另外指示，否則利用Laurel WS-650-23B旋轉塗佈機及Tokyo Electron Ltd. Clean Track ACT-8. Nordson (300 Nordson Dr. M/S 47 Amherst, OH 44001 U.S.A進行膜之旋塗及烘烤。使用MARCH蝕刻機用於不含Si結構域之電漿蝕刻。分別在AMAT (Applied Materials, Inc. 3050 Bowers Avenue P.O. Box 58039 Santa Clara, CA 95054-3299 U.S.A.) NanoSEM 3D及Hitachi (Hitachi High Technologies America Inc. 10 North Martingale Road, Suite 500 Schaumburg, Illinois 60173-2295) S-5500上獲取俯視影像及橫截面影像。表1給出所用化合物及溶劑之縮寫字列表。在此表中，「Sigma-Aldrich」係指位於3050 Spruce St., St. Louis, Missouri 63103之「Sigma-Aldrich Corporation」；「Synquest」係指位於13201 Rachael Blvd, Rt 2054之「SynQuest Laboratories, Inc.」，「Exfluor」係指位於2350 Double Creek Dr, Round Rock, TX 78664之「Exfluor Research Corporation」，「Perstorp Chemicals」係指位於Neptunigatan 1, 211 20 Malmö, Sweden之「Perstorp Specialty Chemicals」，「Richman Chemicals」係指位於768 North Bethlehem Pike, PA 19002之「Richman Chemicals Custom Solutions」。塗佈SiArc溶液(Shin Etsu SHB A-940 L35)係自Shin-Etsu Chemical Co., Ltd (Tokyo 100-0004, Japan)購得。 塗佈溶液AZEMBLYÔ NLD-089、AZEMBLYÔ NLD-208D、AZEMBLYÔ NLD-128及AZEMBLYÔ NLD-127係自AZ Electronic Materials (Somerville, NJ)獲得。表 1

縮醛保護之BISMPA單體(AcBISMPA) (21)係如先前所報告製備(ACS Macro Letters, 2(1), 19-22；2013)。

(21) 三甲基矽基苯乙烯(TMSS) (22)係如先前所報告合成(Macromolecules 2009, 42, 4614-4621)。

(22)實例 1 ：二官能直鏈全氟烷烴利用 ATRP 起始劑及羥基官能基之合成：

方案 3 關於由嵌段A (PS)及嵌段B (TMC)組成經由直鏈全氟烷烴接合連接之聚苯乙烯-b -(直鏈全氟烷烴)-聚(碳酸三甲酯) (方案3)之合成，使用2-溴-2-甲基丙醯溴選擇性酯化十六氟-1,10-癸二醇，如以下所給出：

在配備有磁力攪拌棒、加料漏斗、溫度計及鼓泡管之250 ml圓底燒瓶中，在氮氣下將9.5 g (20.56毫莫耳)預先乾燥之2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-十六氟-1,10-癸二醇添加至50 ml無水DCM。當冷卻時，於10℃下將2.23 g (22毫莫耳)三乙胺傾倒於燒瓶中。然後，於-8℃至-3℃下將4.6 g (20毫莫耳)於30 ml DCM中之2-溴-2-甲基丙醯溴逐滴添加至反應粗製物。將反應物於室溫下攪拌20小時。將150 ml添加至反應粗製物，然後藉由過濾分離沈澱並鑑別為TEA·HBr之鹽。將母液在真空下蒸發。藉由NMR及GC-MS分析粗製物(圖3及4)。彼時未實施任何純化步驟。 粗製產物之¹ H NMR及GC-MS之結果指示形成單、雙酯及極少未反應二醇以及TEA·HBr。實例 2. 薄片成形聚苯乙烯 -b -( 直鏈全氟烷烴 )- 聚 ( 乳酸交酯 ) 二嵌段共聚物薄膜之形態 將Si基板之清潔表面用51%含PS之刷狀聚合物(AZEMBLY™ NLD-127)藉由在1500 rpm下旋塗並於250℃烘烤2 min、隨後PGMEA沖洗30 sec並於110℃軟烘烤1 min來處理。在表面經處理基板之試件上，將接合改質之聚(苯乙烯-b - (直鏈全氟烷烴)-乳酸交酯) (PS-CH₂ -CF₂ CF₂ CF₂ CF₂ CF₂ CF₂ C₂ H₄ -PLA, 11.3k-12.8k, Vf PLA = 0.49,L ₀ ~ 22 nm)之1% PGMEA溶液以3000 rpm旋塗並分別在在周圍氣氛中於110℃、140℃及170℃退火5 min。於NLD-127薄膜上形成相分離、垂直定向薄片狀結構域，此在底層與嵌段共聚物膜之界面處為PS及PLA奈米結構域提供化學非優先表面。亦觀察到維持以垂直方式薄片形態之指紋晶粒大小生長，此指示接合改質增強對嵌段共聚物之形態垂直度之熱耐受性。在O2 RIE處理後，具有接合全氟烷烴之嵌段共聚物薄膜試樣之對應AFM影像(圖5)及無接合改質之SEM影像(圖6)在下文給出。比較實例 3 ：薄片成形聚苯乙烯 -b - 聚 ( 乳酸交酯 ) 二嵌段共聚物薄膜之形態 將Si基板之清潔表面用50%含PS之刷狀聚合物(AZEMBLY™ NLD-361)藉由在1500 rpm下旋塗並於250℃烘烤2 min、隨後PGMEA沖洗30 sec並於110℃軟烘烤1 min來處理。在表面經處理基板之試件上，將聚(苯乙烯-b -乳酸交酯) (PS-b -PLA, 8k-9k, Vf PLA = 0.50,L ₀ ~ 19 nm)之1% PGMEA溶液以3000 rpm旋塗並分別在周圍氣氛中於120℃、140℃及170℃退火5 min。僅藉由於120℃退火，相分離薄片狀結構域垂直定向，而在高於140℃之溫度下退火導致形成島/孔洞，此係平行薄片形態之典型特徵。此結果指示，用於PS-b -PLA之退火製法在無接合改質之情形下極大地受限。對應SEM影像於圖6中給出。As used herein, unless otherwise indicated, an aryl refers to an aromatic moiety having one attachment point (eg, phenyl, fluorenyl, naphthyl, and the like). In addition to the attachment points, the aryl group can be substituted with an alkyl group, an aryl group or a halogen group (e.g., F, Cl, I, Br). By aryl group is meant an aromatic moiety having more than one attachment point. In addition to the attachment points, the extended aryl group can be substituted with an alkyl group, or a halo group (e.g., F, Cl, I, Br) or an aryl group. Alkyl refers to a straight chain, branched or cyclic alkane moiety having an attachment point (e.g., methyl, ethyl, propyl, n-butyl, t-butyl, cyclohexyl, and the like). In addition to the attachment points, the alkyl group can be substituted with an alkyl group, an aryl group or a halogen group (e.g., F, Cl, I, Br). An alkylene group refers to a linear, branched or cyclic alkane moiety having more than one attachment point. In addition to the attachment points, alkylene groups can be substituted with alkyl, aryl or halo groups (e.g., F, Cl, I, Br). The fluorine moiety designates a fluorine group (i.e., F) or a partially or fully fluorinated hydrocarbon group, wherein the hydrocarbon group is an aromatic moiety, an aliphatic moiety, or a mixture thereof, wherein the moiety may also contain a hetero atom other than fluorine. As a hanging group or as part of a chain or ring structure. Fluoroaryl, fluoroaryl, fluoroalkyl, fluoroalkyl refers to such moieties that are partially or fully fluorinated as described above. The nitrogen-containing heterocyclic moiety refers to a 5-8 membered cyclic hydrocarbon containing one or more nitrogen atoms in the ring, and the rings may be completely saturated or contain an unsaturated moiety (for example, a nitrogen-containing heterocyclic compound such as pyrrole). Pyridine, pyrrole, imidazolium, imidazole, 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, 4H-1,2,4- Triazole, pyridine and the like). The oxygen-containing heterocyclic moiety refers to a 5-8 membered cyclic hydrocarbon containing one or more oxygen atoms in the ring (eg, tetrahydrofuran, furan, oxetane, pyran, dioxolane, dioxane, and And so on). A sulfur-containing heterocyclic moiety refers to a 5-8 membered cyclic hydrocarbon containing one or more sulfur atoms in the ring (eg, tetrahydrothiophene, thiophene, thiopyran, thiopyran, dithiocyclohexane, dithiazide). Alkene and the like). When a heterocyclic moiety containing oxygen, sulfur or nitrogen is attached via another moiety, the moiety is preceded by a (containing a heterocyclic moiety of). For example, the moiety to which the oxygen-containing heterocyclic moiety is attached via the oxy (-O-) moiety will be referred to as "oxy-(oxygen-containing heterocyclic moiety)". The fluorenyl group refers to a group of the formula -C(=O)R wherein R is an alkyl group. The fluorine-containing linear hydrocarbon group, the fluorine-containing branched hydrocarbon group, and the fluorine-containing cyclic hydrocarbon group refer to a linear, branched or cyclic moiety or a fully fluorinated alkyl group, which may also contain an olefin. An unsaturated moiety, an extended aryl moiety or an aryl substituent. a fluorine-containing linear alkyl ether group, a fluorine-containing branched alkyl ether group, or a fluorine-containing cyclic alkyl ether group means a linear, branched or cyclic ether containing one or A linear, branched or cyclic, partially or fully fluorinated alkyl or alkyloxy moiety of a plurality of ether moieties which may also contain an olefinic unsaturation, an extended aryl moiety or an aryl substituent. Si₁ -Si₈ The oxoxane moiety is meant to contain (--Si(alkyl)₂ -O)_N- A portion of an alkyl group wherein the alkyl moiety can be a linear, branched or cyclic alkyl moiety and n specifies the number of oxane moieties in the chain, wherein n = 1 to 8. With Si₁ -Si₈ a linear hydrocarbon moiety of a siloxane suspension group having Si₁ -Si₈ a branched hydrocarbon moiety of a siloxane suspension group having Si₁ -Si₈ The cyclic hydrocarbon moiety of the oxane suspension group refers to the attachment of Si as defined above, respectively.₁ -Si₈ A linear, branched or cyclic alkyl moiety of a oxane moiety. Carboxane refers to an alkyl moiety in which at least one carbon atom has been replaced by a halogen atom. A linear hydrocarbon moiety having a carbon decane suspension group, a branched hydrocarbon moiety having a carbon decane suspension group, and a cyclic hydrocarbon moiety having a carbon decane suspension group respectively mean a linear chain to which a carbon decane moiety is attached as described above , having a branched or cyclic alkyl moiety. Decane means Si_n H_2n+1 section. Terpene means Si_n H_2n section. The linear hydrocarbon moiety having a decane suspension group, the branched hydrocarbon moiety attached to the decane suspension group, and the cyclic hydrocarbon moiety having a decane suspension group respectively mean a linear chain having a decane suspension group attached thereto Chain or cyclic alkyl moiety. The term "-b-" refers to "-block-" and specifies the monomer repeating unit that forms the block copolymer. The term "P" means "poly" in the presence of a single abbreviation, which designates a polymerized monomer (eg, PS designates poly(styrene), because S is an abbreviation for styrene definition). The term "JBCP" (block copolymer to which a surface active moiety is bonded) is an abbreviation, which means an incorporation of the invention having a bonding group having a structure (1a) or (1b) having a surface active moiety as defined herein. Segment copolymer. The term "surface-active conjugate group" refers to the X moiety of structures (1a) and (1b) as defined herein. The term "phase separable" is used to describe a phase-separable polymer block in a block copolymer and refers to the property of the blocks to be separated from one another when the block domains are insoluble with one another when cast into a film. This phase separation of the polymer block domains in the film can be spontaneously revealed in solution or alternatively in a cast film or by heat treatment (e.g., heating) casting of the film. When the film is cast into a film, if the polymer block polymer film is plasticized by solvent vapor, phase separation can also occur at room temperature. Term V_f Means the volume fraction and indicates the volume fraction of the block when further annotated with the abbreviation of the polymer repeating unit block (for example, PS for polystyrene) (eg V_fPS Represents the volume fraction of this block in a block copolymer containing a polystyrene block). The term Lo is a periodicity of the domain of the self-assembled pattern of BCP. In one embodiment, the present invention is directed to novel block copolymers wherein the block copolymer comprises a diblock copolymer having a divalent bonding or linking group (X). The copolymer has a first polymer block (block A) and a second polymer block (block B). In a particular embodiment, block B has a chemical structure different from block A and is capable of segregating from block A. In certain embodiments, the divalent linking group X covalently links the terminal repeating unit of block A to the terminal repeating unit of block B. In certain embodiments, the block copolymer has the structure (1a):

(1a) wherein, A is a block polymer chain, a B-based block polymer chain, wherein A and B are chemically different covalently bonded polymer chains, and the tether phase is separable; X is in A polymer Between the block and the B polymer block, a divalent linking group selected from the group consisting of fluorine-containing moieties, Si-containing groups₁ -Si₈ A portion of a siloxane, a hydrocarbon portion having at least 18 carbons, and combinations thereof, and further wherein X has a surface energy less than block A and less than block B. In certain embodiments, the block copolymer has the structure (1b):

(1b) where E¹ Is the monovalent first end group, E² Is a monovalent second terminal group, P' represents the first polymer chain of the first block (block A) of the block copolymer, and P'' represents the second block of the block copolymer ( a second polymer chain of block B), and X is a terminal repeating unit of P' bonded to a divalent linking group of a terminal repeating unit of P'', wherein X contains 1-24 fluorines, and X Each of the iso-fluorines is linked to the backbone carbon of the block copolymer. In certain embodiments, the block copolymer has the structure (1b):

(1b) where E¹ Is the monovalent first end group, E² Is a monovalent second terminal group, P' represents the first polymer chain of the first block (block A) of the block copolymer, and P'' represents the second block of the block copolymer ( a second polymer chain of block B), and X is a terminal repeating unit of P' bonded to a divalent linking group of a terminal repeating unit of P'', wherein X comprises a perfluoroalkane having 1-24 carbons And X is linked to the backbone carbon of the block copolymer either directly or via an alkane spacer consisting of 1-6 carbons at both ends. In some embodiments, E¹ -P' together form block A and E² -P'' together form block B. In some embodiments, E¹ -P' together form block B and E² -P'' together form block A. In some embodiments, E¹ And E² Each is independently selected from the group consisting of H, hydroxy, halo, alkyl, aryl and fluorenyl. In a specific embodiment, E¹ Or E² One of them is H and E¹ With E² The other one is based on 醯. In a specific embodiment, E¹ Or E² One of them is a halogen group and E¹ With E² The other one is based on 醯. In a specific embodiment, E¹ Or E² One of them is Br and E¹ With E² The other one is based on 醯. In a specific embodiment, E¹ Or E² At least one of them is a halogen group. In a specific embodiment, E¹ Or E² At least one of them is Br. In a specific embodiment, E¹ Or E² At least one of them is a base. In a specific embodiment, E¹ Or E² At least one of them is an ethyl group. In certain embodiments, the first block comprises a copolymer of styrene and trimethyldecyl styrene. In some embodiments, X has the following structure:

Where n' is an integer having a value of 1-12, 2-10 or 2-7. In some embodiments, X has the following structure:

Where n'' is an integer having a value of 1-5, 1-4 or 1-3. In a particular embodiment, X can be a divalent linking group that covalently links the terminal repeating unit of block A to the terminal repeating unit of block B, wherein X comprises 1-24, or 2-10 or 2-7 Fluorine. In a particular embodiment, each of the fluorines of X is linked to the backbone carbon of the block copolymer. Specific examples of the fluorine-containing portion a), the Si1-Si8 oxane portion b), and the hydrocarbon portion c) having at least 18 carbons are as follows: a) X-based fluorine-containing linear hydrocarbon group, fluorine-containing a branched hydrocarbon group, a fluorine-containing linear alkyl ether group, a fluorine-containing branched alkyl ether group, and a mixture thereof, b) X-based Si₁ -Si₈ a oxoxane moiety, a carbon decane, a decene, and mixtures thereof, and c) a X-line having a linear hydrocarbon group of at least 18 carbons and a branched hydrocarbon having at least 18 carbons. In some aspects, X is a fluorinated alkyl group of formula (C-1):

Wherein the skeleton carbon of each carbon-based block copolymer linked to fluorine, n' has an integer of 2-12, 2-10 or 2-7, and m' has 1-5, 1-4 or 2 An integer of a value of -3, and k' is an integer having a value of 1-5, 1-4, or 2-3. In some aspects, the divalent linear fluorinated oxirane group of formula X (C-2):

(C-2), wherein each carbon linked to fluorine is a skeleton carbon of the block copolymer, and n'' is an integer having a value of 1-5, 1-4 or 2-3. In one aspect of the invention, the joint portion X in the structures (1a) and (1b) has less than about 30 mN m^-1 Surface energy. In a more specific embodiment, the joint portion has a relationship of 30 mN m^-1 With 10 mN m^-1 Between, preferably between 25 mN m^-1 With 14 mN m^-1 The surface energy between. In general, block copolymers suitable for the structures (1a) and (1b) of the invention have a weight average molecular weight in the range of from about 3,000 g/mol to about 500,000 g/mol (M)._w And a number average molecular weight of about 1,000 to about 60,000 (M)_n And a polydispersity of from about 1.01 to about 6, or from 1.01 to about 2 or from 1.01 to about 1.5 (M)_w /M_n ) (PD). Other embodiments are those in which the a is an integer of 1 or 2 in the structures (1a) and (1b). Another embodiment is where b is an integer from 1 to 2. In another embodiment of the block copolymer having structure (1a) or (1b), M_n It is in the range of 4,000 to 150,000 and the polydispersity (PD) is in the range of 1.01 to 5.0, more preferably 1.01 to 2.0. In another embodiment of the invention, one of the block A or the block B comprises repeating units that are resistant to the plasma etching techniques typically employed in the fabrication of IC devices relative to other blocks; and other blocks It is rapidly etched under the same plasma etching conditions or can be removed by chemical or photochemical processes. This property allows the pattern of the self-assembled domain pattern to be transferred into the substrate when the materials are formulated with a solvent and applied to the patterned substrate. If self-assembly is performed on a patterned substrate, it is guided self-assembly. The process of guided self-assembly of novel block copolymers can be carried out, for example, using a pattern epitaxy process or a chemical epitaxy process. Another embodiment of the present invention is that the block A in the structure (1a) or (1b) comprises a unit derived from an ethylenically unsaturated polymerizable monomer or a ring-opening polymerization (ROP) derived from a cyclic monomer. a unit, and wherein the block B comprises a unit derived from an ethylenically unsaturated polymerizable monomer or a ring-opening polymerization (ROP) derived from a cyclic monomer, and further wherein the polymer blocks A and B are different from each other and The phase can be separated. Another aspect of the invention is wherein the block A or B is derived from a vinyl polymerizable monomer. In other embodiments, each of block A and block B is independently derived from a vinyl aryl monomer, a lactone, an intrinsic amine, an epoxide, a cyclic carbonate monomer, or an olefinic system. Saturated polymerizable monomer. In a particular embodiment, block A and block B are chemically distinct and the phases are separable (eg, forming a pattern of phase segregated alternating domains). In certain embodiments, block A comprises an olefinic repeating unit of formula (A-1):

(A-1), where i) each R^w Is a monovalent group selected from the group consisting of H, F, methyl, ethyl, and trifluoromethyl (*-CF3), and ii) each R^d A monovalent group comprising an aromatic ring linked to carbon 1. In certain embodiments, block A comprises an olefinic repeat unit selected from the group consisting of

And their combinations. In certain embodiments, block B comprises an aliphatic carbonate repeating unit. In certain embodiments, the aliphatic carbonate repeating unit comprises a pendant ester group. In a particular embodiment, the aliphatic carbonate repeating unit has the structure of formula (B-4):

(B-4), where R^g A monovalent hydrocarbon group containing 1-20, 1-10 or 2-5 carbons. In some embodiments, R^g It is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl and benzyl. In a specific embodiment, R^g Is a methyl group. In certain embodiments, block B comprises an aliphatic ester repeat unit. In certain embodiments, the aliphatic ester repeating unit has a structure

Wherein j' is an integer having a value of 0-4, 0-3 or 1-2. In certain embodiments, the aliphatic ester repeating unit has a structure

. In certain embodiments, block B comprises an aliphatic ether repeating unit. In a particular embodiment, the aliphatic ether repeating unit is selected from the group consisting of ethylene oxide, propylene oxide, ring-opening glycidyl ether, and combinations thereof. In certain embodiments, block B is a homopolymer comprising a repeating unit selected from the group consisting of

Another embodiment of the structure (1a) or (1b) wherein the linking group X in the structure (1a) or (1b) has 3 to 7 polyvalent groups selected from a polyvalent hetero atom and containing a hetero atom A portion of the attachment point of a polyvalent organic group, a polyvalent organic group containing a hetero atom, and combinations thereof. A more specific example of the X part is C₁ -C₃₀ Linear alkyloxy moiety, C₃ -C₃₀ Branched alkyloxy moiety, C₁ -C₂₀ Urethane-linear alkyl moiety (-N(R)₁₁ )-C(=O)-O-straight chain alkyl), C₃ -C₃₀ Urethane-branched alkyl moiety (-N(R)₁₁ )-C(=O)-O-having a branched alkyl moiety), C₁ -C₂₀ Urea-straight chain alkyl moiety (-N(R)₁₁ )-C(=O)-N(R₁₁ )-straight chain alkyl group, C₃ -C₃₀ Urea-branched alkyl moiety (-N(R)₁₁ )-C(=O)-N(R₁₁ ) - with a branched alkyl moiety), C₁ -C₂₀ Thiourea-linear alkyl moiety (-N(R)₁₁ )-C(=S)-N(R₁₁ )-straight chain alkyl group, C₃ -C₃₀ Thiourea - branched alkyl moiety (-N(R)₁₁ )-C(=S)-N(R₁₁ )--with a branched alkyl moiety), where R₁₁ Hydrogen or C₁ To C₄ Alkyl; 1,2,3-triazole moiety, 1,2,3-triazole C₁ -C₃₀ Alkyl moiety, 1,2,3-triazole C₃ -C₃₀ Branched alkyl moiety, 1,2,3-triazole C₃ -C₃₀ Cyclic alkylene moiety, 1,2,3-triazole C₁ -C₃₀ Alkyloxy moiety, 1,2,3-triazole C₃ -C₃₀ Branched alkyloxy moiety, 1,2,3-triazole C₃ -C₃₀ Cyclic alkylene moiety, C₃ -C₃₀ Cycloalkoxy moiety, C₃ -C₃₀ Linear alkyloxycarbonyl moiety, C₅ -C₃₀ Branched alkyloxycarbonyl moiety, C₃ -C₃₀ Cycloalkoxycarbonyl moiety, C₁ -C₃₀ Linear fluoroalkyl group, C₃ -C₃₀ Branched fluoroalkyl group, C₆ -C₃₀ Cyclic fluoroalkyl group, C₆ -C₃₀ Extending the base part, C₆ -C₃₀ Fluorinated aryl moiety, C₅ -C₃₀ Oxyalkyleneoxycarbonylalkylene moiety, C₂ -C₃₀ Alkyloxyalkylene moiety, aryl substituted C₈ -C₄₂ Alkyloxy moiety, aryl substituted C₈ -C₄₂ Alkyloxyalkylene moiety, C₈ -C₄₂ Aryl substituted alkyl moiety, C₇ -C₃₀ Extending alkyl aryl moiety, C₇ -C₃₀ Fluorine alkyl extended aryl moiety and combinations thereof. A more specific embodiment of this aspect is when the X moiety is selected from C₅ -C₃₀ Oxyalkyleneoxycarbonylalkylene moiety, C₂ -C₃₀ Alkyloxyalkylene moiety, aryl substituted C₈ -C₄₂ Alkyloxy moiety, aryl substituted C₈ -C₄₂ Alkyloxyalkylene moiety or C₈ -C₄₂ When the aryl group is substituted with an alkyl moiety. Other embodiments of structure (1a) or (1b) are those in which a portion of the X-based fluorine-containing hydrocarbon group, such as a linear C₁ -C₁₀ Fluorine alkyl, C₃ -C₁₀ Branched fluoroalkylene, alkyl fluoroalkyl (-(CH)₂ )_q (CF₂ )_r -CF₂ -), CFH-containing alkyl fluoroalkyl (-(-CH)_2- )_q (CHF)_Q2 (CF₂ )_r -CF₂ -), alkyl fluoroether-fluoroalkyl----CH_2- )_q (-CF₂ -O-)_s (-CF₂ CF₂ -O-)_t (CF₂ )_u CF₂ -, alkyl fluoroether-fluoroalkyl (CH) containing CHF_2- )_q (CHF)_Q2 (-CF₂ -O-)_s (-CF₂ CF₂ -O-)_t (CF₂ )_u CF₂ - or have a part of structure (2)

(2) where q is an integer from 0 to 10, q2 is an integer from 1 to 10, r is an integer from 1 to 10, s is an integer from 0 to 10, t is an integer from 1 to 10, and u is between 0 and An integer of 10, x is 1 to 5, y is 1 to 5, and P is a direct bond, C₁ To C₄ Alkyl or -CH₂ -CH₂ -(CF₂ )₄ -section. Another aspect of the invention is wherein the structure (1a) or (1b) has an X moiety comprising an alkyloxycarbonylalkylene moiety. In this aspect of the invention, the novel block copolymers can be prepared by atom-transfer radical-polymerization (ATRP) initiators or ring-opening polymerization (ROP) initiators. The block copolymer having the structure (1a) or (1b) and the above substructure can be produced by various methods, for example, by using atom-transfer radical-polymerization (ATRP) and ring-opening polymerization (ROP). A block copolymer is prepared, and a block copolymer is prepared by using a 1,1-stilbene (DPE) derivative as an initiator and a blocking agent in anionic block polymerization. Scheme 1 shows the synthesis of an ATRP and ROP initiator comprising an oxy-X-carbonylalkyl moiety. This initiator can be used to produce a novel block copolymer of structure (1a) or (1b). Similarly, other types of X moieties can be attached to the initiators by using a suitable alcohol containing a suitable X moiety, such as a fluorine-containing linear hydrocarbon group, a fluorine-containing branched hydrocarbon group. a fluorine-containing linear alkyl ether group, a fluorine-containing branched alkyl ether group or a mixture thereof, Si₁ -Si₈ A oxane moiety, a carbon decane, a decene or a linear hydrocarbon chain having more than 18 carbons.

Program 1 A non-limiting example of the synthesis of a linear bonded A-B diblock copolymer having a bonding configuration X (eg, a linear perfluoroalkane and a linear perfluoroether) is shown in Scheme 2. As shown, block A is styrene, but other polymer blocks (e.g., substituted polystyrene) can be used. Similarly, as shown, block B is trimethyl carbonate (TMC), but other polymer blocks (eg, polylactide (PLA), polycaprolactone (PCL), and trimethyl carbonate) can be used. ).

Scheme 2 A diol can be used to selectively convert one hydroxyl group to an atom transfer radical polymerization initiator. This can be carried out by reacting a diol with 2-bromo-2-methylpropionamidine bromide in the presence of triethylamine in dichloromethane. The selectivity for monofunctionalization can be controlled by the slow addition of 2-bromo-2-methylpropionamidine bromide. By-products such as difunctional and unreacted reagents can be removed by column chromatography techniques. The monofunctional reagents will be used in the context of the ATRP conditions in the literature and are widely used in the literature (see, for example, U.S. Patent Application Serial No. 14/628,002, filed on Jan. Starting styrene monomer in the presence of a composite CuBr. The resulting polystyrene (PS(F)-OH) having a hydroxyl end group will be used for ring-opening anion coordination using a cyclic monomer selected from the group consisting of cyclic carbonates, D, L-lactide, lactones and the like. Polymerization to synthesize the second block. The conditions used to polymerize the monomers using hydroxyl-containing starters are well known in the literature. The use of the macromolecular initiator PS(F)-OH under the conditions described in the literature will result in the desired diblock copolymer having the desired linker X moiety. The formation of a polymer block containing units derived from a cyclic monomer by ring-opening polymerization of a novel block copolymer having the structure (1a) or (1b) can be used for one of the blocks having been opened by The techniques set forth in the other types of diblock copolymers derived from the ring polymerization are disclosed, for example, in U.S. Patent No. 8,642,086, the disclosure of which is incorporated herein by reference. It will be appreciated that other coupling reactions known in the art can be employed to join the two different polymer blocks together via the linked X moiety of structure (1a) or (1b). In the block copolymer of structure (1a) or (1b), block A may comprise a derivative derived from an alkyl vinyl monomer, an alkyl methacrylate monomer, an alkyl acrylate monomer, a lactone. a portion of a unit of a body, an epoxide monomer, an indoleamine monomer, a cyclic carbonate monomer, and the block B may be a moiety comprising a repeating unit derived from a vinyl aryl monomer and further a block thereof The A and B phases are separable. Further, in another embodiment of the present invention, the block A may comprise a unit derived from an ethylenically unsaturated polymerizable monomer which is a vinyl aryl monomer, and the block B may comprise a derivative derived from an acrylate or a unit of a methacrylate-based ethylenically unsaturated polymerizable monomer, or a unit comprising a ring-opening polymerization (ROP) derived from a cyclic monomer selected from a lactone or a cyclic carbonate, and further wherein the block A and The B-phase is separable. In another embodiment, the block copolymer of structure (1a) or (1b) has a block derived from a ring-opening polymerizable monomer. In another embodiment, blocks A and B can be derived from two different ethylenically unsaturated polymerizable monomers, wherein the block A and B phase phase separable moieties. When the polymer block in the novel block copolymer having the structure (1a) or (1b) is derived from a cyclic carbonyl monomer or an ethylenically unsaturated polymerizable monomer, the polymer block may be a homopolymer. Or a random copolymer. Cyclic carbonyl monomers can be stereospecific or non-stereospecific. The formation of a polymer block containing units derived from a cyclic monomer by ring-opening polymerization of a novel block copolymer having the structure (1a) or (1b) can be used for one of the blocks having been opened by The techniques set forth in other types of diblock copolymers derived from ring polymerization are disclosed, for example, as disclosed in US Pat. No. 6,426,086 B2, incorporated herein by reference. Typically, in structure (1a) or (1b), one of the diblock copolymers is resistant to plasma etching while the other block is etched very rapidly under the same conditions, which allows for coating by structure ( The novel polymer of 1a) or (1b) is transferred to the substrate by a self-assembled pattern pattern formed by annealing. This self-assembly is guided on a patterned substrate using patterned epitaxy or chemical epitaxy. The ethylenically unsaturated monomer which may be employed in forming the polymer block in the novel block polymer having the structure (1a) or (1b) may comprise a derivative derived from a vinyl aryl group, an alkyl vinyl monomer, A unit of an alkyl acrylate monomer or an alkyl acrylate monomer. The polymer block in the novel block copolymer having the structure (1a) or (1b) derived from an unsaturated monomer may be a homopolymer or a random copolymer. The olefinic unsaturation can be stereospecific or non-stereospecific. Non-limiting examples of alkyl vinyl compounds, alkyl acrylates or alkyl methacrylates useful in making the blocks of the novel block copolymers of the present invention are those in which the alkyl group is: C₁ -C₄ Fluoroalkyl, C₁ -C₁₀ Linear alkyl moiety, C₁ -C₄ Hydroxyfluoroalkyl, C₂ -C₁₀ -alkyloxyalkylene, C₁ -C₁₀ -hydroxylalkyl, C₃ -C₂₀ Branched alkyl, C₃ -C₂₀ Cyclic alkyl, C₂ -C₂₀ Carboxyalkyl, C₃ -C₂₀ Alkyloxycarboxyalkyl or C₃ -C₂₀ Alkyloxycarboxyoxyalkylene; other substituents which do not contain a refractory element are also possible. The alkyl group attached to the carboxyl moiety in the examples may also be an acid cleavable group capable of releasing a free carboxyl moiety when reacted with a strong acid formed by a thermal acid generator or a photoacid generator (eg, a tertiary ester, Acetal or ketal). If a block derived from an alkyl vinyl compound, an alkyl acrylate or an alkyl methacrylate is used as the etch-resistant block portion, the alkyl group may be substituted with a moiety containing a refractory element, such as C.₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyltin or C₃ -C₂₀ Trialkyl titanium base. Non-limiting examples of anti-etching block vinyl aryl compounds useful in making the novel block copolymers of structure (1a) or (1b) of the present invention are unsubstituted styrene, unsubstituted vinyl naphthalene , unsubstituted vinyl hydrazine, unsubstituted vinyl hydrazine, and the like; or aryl moiety containing one or more of the following substituents: for example, C₁ -C₂₀ Alkyl, C₁ -C₂₀ Hydroxyalkyl, C₂ -C₁₀ -alkyloxyalkylene, C₁ -C₄ Fluoroalkyl, C₁ -C₄ a hydroxyfluoroalkyl group, a hydroxyl group, a hydroxyl group blocked by an acid labile group, a carboxyl group, a carboxyl group blocked with an acid labile group (the acid cleavable moiety is present in the film by a thermal acid generator) Or a strong acid formed by a photoacid generator can release a free hydroxyl group or a free carboxyl group), a fluoroalcohol group, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyltin, C₃ -C₂₀ Trialkyl titanium base, C₂ -C₂₀ Alkylcarbonyl, C₂ -C₂₀ Alkylcarbonyloxy, C₁ -C₂₀ Alkoxy or C₉ -C₃₆ Paraxyl (trialkylsulfonyl) fluorenyl; unsubstituted vinyl naphthalene and vinyl naphthalene substituted by C: C₁ -C₂₀ Alkyl, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyltin, C₃ -C₂₀ Trialkyl titanium base, C₂ -C₂₀ Alkylcarbonyl, C₂ -C₂₀ Alkylcarbonyloxy, C₁ -C₂₀ Alkoxy, C₉ -C₃₆ Paraxyl (trialkylsulfonyl) fluorenyl; vinyl fluorene; vinyl hydrazine substituted by C:₁ -C₂₀ Alkyl, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyltin, C₃ -C₂₀ Trialkyl titanium base, C₂ -C₂₀ Alkylcarbonyl, C₂ -C₂₀ Alkylcarbonyloxy, C₁ -C₂₀ Alkoxy, C₉ -C₃₆ Paraxyl (trialkylsulfonyl) fluorenyl; vinyl fluorene; vinyl hydrazine substituted by C:₁ -C₂₀ Alkyl, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyltin, C₃ -C₂₀ Trialkyl titanium base, C₂ -C₂₀ Alkylcarbonyl, C₂ -C₂₀ Alkylcarbonyloxy, C₁ -C₂₀ Alkoxy or C₉ -C₃₆ Paraxyl (trialkylsulfonyl) fluorenyl or the like. In one embodiment of the novel diblock polymer having structure (1a) or (1b), two polymer blocks are derived from two different ethylenically unsaturated monomers, one block being resistant to plasma etching And derived from a vinyl aryl compound, a vinyl alkyl group, an alkyl methacrylate or an alkyl acrylate, wherein the alkyl group contains the refractory element as described above, and the other block is rapidly etched using the same plasma chemistry. For example, a block derived from an alkyl vinyl group, an alkyl acrylate, an alkyl methacrylate, wherein the alkyl moiety is free of a refractory element. In another embodiment of the novel diblock polymer having structure (1a) or (1b), one polymer block is etch resistant and is derived from a vinyl aryl compound, a vinyl alkyl group, a methacrylic acid An alkyl ester or an alkyl acrylate wherein the alkyl group contains a refractory element as described above, and another block which is rapidly etched using the same plasma chemistry is derived from a cyclic monomer (eg, epoxide, lactone, yttrium) Ring-opening polymerization of an amine or a cyclic carbonate). The cyclic monomers may contain one or more substituents or aromatic rings which are free of refractory elements. Possible non-limiting examples of substituents are hydroxyl, C₁ -C₂₀ Alkyl, C₁ -C₂₀ Hydroxyalkyl, C₂ -C₁₀ -alkyloxyalkylene, halo (F, Cl, Br, I), haloalkyl, cyano, C₁ -C₄ Fluoroalkyl, C₁ -C₄ a hydroxyfluoroalkyl group, a hydroxyl group, a hydroxyl group blocked by an acid labile group, a carboxyl group, a carboxyl group blocked by an acid labile group, a carboxyl group alkyl group, and a carboxyl group deuterated by an acid labile group. a group, an alkyloxycarbonyl group, an alkylcarbonyl group, an alkyl group having a double carbon bond or a triple carbon bond, and other substituents containing no refractory element. Specific examples of lactones which can be used as a precursor of one of the blocks in the novel block copolymer of structure (1a) or (1b) are as follows: β-propiolactone, γ-butyrolactone, δ -valerolactone, ε-caprolactone, β-butyrolactone, γ-valerolactone, pivalolactone, 1,5-dioxepeptan-2-one, 5-(benzyloxy) Oxecycloheptan-2-one; cyclic carbonate selected from the group consisting of trimethylene carbonate, tetramethylene carbonate, pentamethylene carbonate; glycosides, 2-bromo-2-methylpropionic acid 7- Sideoxyoxepane-4-yl ester, 5-phenyloxacycloheptan-2-one, 5-methyloxacycloheptan-2-one, 1,4,8-trioxa (4 , 6) spiro-9-undecane, 5-(benzyloxymethyl)oxacycloheptan-2-one, 3-hydroxy-2-(hydroxymethyl)-2-methylpropionic acid 7- Sideoxyoxetan-4-yl ester, (Z)-6,7-dihydrooxeene-2(3H)-one, D-lactide, L-lactide, internal Racemic-lactide or such materials containing other substituents such as hydroxyl, C₁ -C₂₀ Alkyl, C₁ -C₂₀ Hydroxyalkyl, C₂ -C₁₀ -alkyloxyalkylene, halo (F, Cl, Br, I), haloalkyl, cyano, C₁ -C₄ Fluoroalkyl, C₁ -C₄ a hydroxyfluoroalkyl group, a hydroxyl group, a hydroxyl group blocked by an acid labile group, a carboxyl group, a carboxyl group blocked by an acid labile group, a carboxyl group, an alkyl group, and a carboxyl group blocked by an acid labile group. An alkyl group, an alkyloxycarbonyl group, an alkylcarbonyl group, an alkyl group containing a double or triple carbon bonded refractory element, such as C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyltin or C₃ -C₂₀ Trialkyl titanium base. Specific examples of the carbonate which can be used as a precursor of one of the blocks in the novel block copolymer of the structure (1a) or (1b) are as follows: trimethylene carbonate, tetramethylene carbonate, Pentamethyl carbonate, 5-methyl-2-oxo-1,3-dioxan-5-carboxylic acid, 5-methyl-2-oxo-1,3-dioxane-5 - methyl formate, 5-methyl-2-oxo-1,3-dioxane-5-carboxylic acid tert-butyl ester, 5-methyl-2-oxo-1,3-di Ethoxy-5-carboxylate, 5-methyl-2-oxo-1,3-dioxan-5-carbonyl chloride, 5-methyl-2-oxo-1,3-dioxin Benzyl-5-formic acid benzyl ester, 5-methyl-2-oxo-1,3-dioxane-5-carboxylic acid 2-(tetrahydro-2H-pyran-2-yloxy)ethyl Ester, 5-methyl-2-oxo-1,3-dioxane-5-carboxylic acid 2,2,3,3,4,4,5,5,6,6,7,7,7- Decrohyl heptyl ester, 5-methyl-2-oxo-1,3-dioxane-5-carboxylic acid 2,2,2-trifluoroethyl ester, 5-methyl-2-oxooxy 5-1,3-dioxane-5-carboxylic acid prop-2-ynyl ester, 5-methyl-2-oxo-1,3-dioxane-5-carboxylic acid allyl ester, 5- Methyl-2-oxo-1,3-dioxane-5-carboxylic acid 2-(2-methoxyethoxy)ethyl ester, 5-methyl-2-oxooxy-1,3 - Dioxane-5-carboxylic acid 3-( Tert-butylthio)propyl ester, 5-methyl-2-oxo-1,3-dioxane-5-carboxylic acid 2-(t-butoxycarbonylamino)ethyl ester, 5 2-methyl-2-oxo-1,3-dioxane-5-carboxylic acid 2-(pyridin-2-yldihydrothio)ethyl ester, 5-methyl-2-oxooxy-1 , 3-dioxane-5-carboxylic acid 4-(hydroxymethyl)benzyl ester, 4-(5-methyl-2-oxo-1,3-dioxan-5-carbonyloxy)hexa Hydropyridine-1,3-carboxylic acid tert-butyl ester, N-benzyl-5-methyl-2-oxo-1,3-dioxan-5-carboxamide, N-isopropyl-N, 5-dimethyl-2-oxo-1,3-dioxane-5-carboxamide, 5,5-dimethyltrimethylene carbonate (5,5-dimethyl-1,3 -dioxa-2-one), 5-methylmethylene carbonate (5-methyl-1,3-dioxan-2-one), 5,5-diethyltrimethylene carbonate (5,5-Diethyl-1,3-dioxan-2-one), and 5-ethylethyltrimethyl carbonate (5-ethyl-1,3-dioxan-2-one) Or any of these materials containing other substituents such as hydroxyl, C₁ -C₂₀ Alkyl, C₁ -C₂₀ Hydroxyalkyl, C₂ -C₁₀ -alkyloxyalkylene, halo (F, Cl, Br, I), haloalkyl, cyano, C₁ -C₄ Fluoroalkyl, C₁ -C₄ a hydroxyfluoroalkyl group, a hydroxyl group, a hydroxyl group blocked by an acid labile group, a carboxyl group, a carboxyl group blocked by an acid labile group, a carboxyl group, an alkyl group, and a carboxyl group blocked by an acid labile group. An alkyl group, an alkyloxycarbonyl group, an alkylcarbonyl group, an alkyl group containing a double or triple carbon bonded refractory element, such as C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyltin or C₃ -C₂₀ Trialkyl titanium base. Specific examples of epoxides which can be used as precursors of one of the blocks in the novel block copolymer of structure (1a) or (1b) are as follows: propylene oxide, butylene oxide, epoxy B Alkane, styrene oxide, with C₁ -C₂₀ a glycidyl ether of a R group of a hydrocarbon (straight chain, aliphatic, aromatic, branched, etc.), and an epoxy monomer containing ruthenium (for example, having a trimethyl sulfonium group attached to oxygen or carbon (TMS) a suspension group) or any of these materials having other substituents such as hydroxy, C₁ -C₂₀ Alkyl, C₁ -C₂₀ Hydroxyalkyl, C₂ -C₁₀ -alkyloxyalkylene, halo (F, Cl, Br, I), haloalkyl, cyano, C₁ -C₄ Fluoroalkyl, C₁ -C₄ a hydroxyfluoroalkyl group, a hydroxyl group, a hydroxyl group blocked by an acid labile group, a carboxyl group, a carboxyl group blocked by an acid labile group, a carboxyl group, an alkyl group, and a carboxyl group blocked by an acid labile group. An alkyl group, an alkyloxycarbonyl group, an alkylcarbonyl group, an alkyl group containing a double or triple carbon bonded refractory element, such as C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyltin or C₃ -C₂₀ Trialkyl titanium base. Specific examples of the internal guanamine which can be used as a precursor of one of the blocks in the novel block copolymer of the structure (1a) or (1b): β-propionalamine, γ-butylide, Δ-valeroinamide, and ε-caprolactam and such intrinsic amines or other materials having other substituents such as hydroxyl groups, C₁ -C₂₀ Alkyl, C₁ -C₂₀ Hydroxyalkyl, C₂ -C₁₀ -alkyloxyalkylene, halo (F, Cl, Br, I), haloalkyl, cyano, C₁ -C₄ Fluoroalkyl, C₁ -C₄ a hydroxyfluoroalkyl group, a hydroxyl group, a hydroxyl group blocked by an acid labile group, a carboxyl group, a carboxyl group blocked by an acid labile group, a carboxyl group, an alkyl group, and a carboxyl group blocked by an acid labile group. An alkyl group, an alkyloxycarbonyl group, an alkylcarbonyl group, an alkyl group containing a double or triple carbon bonded refractory element, such as C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyl fluorenyl, C₃ -C₂₀ Trialkyltin or C₃ -C₂₀ Trialkyl titanium base. In another embodiment of the novel diblock polymer having structure (1a) or (1b), one polymer block is resistant to etching and is derived from a vinyl aryl compound or an etch-resistant vinyl group, anti-etching An alkyl acrylate, an etch-resistant alkyl acrylate or an etch-resistant substituted cyclic monomer. The etching resistance of the vinyl alkyl group, the alkyl methacrylate, the alkyl acrylate or the substituted cyclic monomer is such that the substituent on the alkyl group or the cyclic monomer contains the refractory element as described above Or it may be provided by an aryl substituent, an arylalkylene group, or an alkylaryl group or a polycyclic alkyl substituent. In another embodiment of the novel block copolymer having structure (1a) or (1b), the ethylenically unsaturated monomer useful for forming polymer block A may comprise units derived from a vinyl aryl monomer. And the polymer block B may comprise units derived from an ethylenically unsaturated polymerizable monomer, a lactone or a cyclic carbonate and further wherein the block A and B phase phases are separable. In this embodiment, the ethylenically unsaturated polymerizable monomer may be selected from acrylate or methacrylate or a ring-opening polymerization (ROP) derived from a cyclic monomer selected from a lactone or a cyclic carbonate. a unit wherein the vinyl aryl group is selected from the group consisting of styrene, 4-methylstyrene, 4-ethylstyrene, 4-n-propylstyrene, 4-isopropylstyrene, 4-正Butylstyrene, 4-trimethyldecylstyrene, 4-cyclohexylstyrene, 4-cyclopentylstyrene, 3-trimethyldecylstyrene, 4-tert-butylstyrene, 4 -isoamylstyrene, 4-methoxystyrene, 4-n-propyloxystyrene, 4-isopropyloxystyrene, 4-n-butyloxystyrene, 4-cyclohexyloxy Styrene, 4-cyclopentyloxystyrene, 4-trimethyldecyloxystyrene, 3-trimethyloxydecylstyrene, 4-tert-butyloxystyrene, 4 -isopentyloxystyrene, 4-trifluoromethylstyrene, 3-trifluoromethylstyrene, 4-trifluoromethyloxystyrene, 3-trifluoromethyloxystyrene, 4 -T-butyloxycarbonyloxystyrene, 4-tert-butyloxycarbonyl Styrene, 4-tert-butoxycarbonyloxystyrene, 4-vinylbenzoic acid, 4-vinylbenzyl alcohol, 4-vinylbenzoic acid methyl ester, α-methylstyrene, 2,4 - dimethyl styrene, 2,5-dimethyl styrene, and 2,4,6-trimethylstyrene, and wherein methacrylate, if present, may be selected from the group consisting of: methacrylic acid Methyl ester, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, Cyclopentyl methacrylate, isodecyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, 2-methacrylic acid Adamantyl ester, ethyl cyclopentyl methacrylate, 2-ethyl-adamantyloxymethyl methacrylate, tricyclomethyline [5, 2, 1, 0^2,6 癸-8-yl ester, 2-oxo-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, 2-carboxyethyl methyl methacrylate, A 2-carboxyethyl ester ethyl acrylate, 2-carboxyethyl propyl methacrylate, 2-carboxyethyl methacrylate butyl acrylate, 2-carboxyethyl methacrylate third Butyl ester, 2-carboxyethyl ester adamantyl methacrylate and 2-hydroxyethyl methacrylate, and if present, the acrylate can be selected from the group consisting of methyl acrylate and ethyl acrylate. Ester, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, isopropyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, isodecyl acrylate, 3-hydroxy-1-acrylate Adamantyl ester, 2-ethyl-2-adamantyl acrylate, 2-adamantyl acrylate, ethyl cyclopentyl acrylate, 2-ethyl-adamantyloxymethyl acrylate, acrylic acid Three rings [5, 2, 1, 0^2,6 癸-8-yl ester, 2-oxo-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 2-carboxyethyl acrylate methyl ester, 2-carboxyethyl acrylate Ethyl ester, 2-carboxyethyl propyl acrylate, 2-carboxyethyl acrylate n-butyl ester, 2-carboxyethyl acrylate tert-butyl ester, 2-carboxyethyl acrylate adamantyl acrylate Ester and 2-hydroxyethyl acrylate. Also in this embodiment, the lactone may be selected from the group consisting of β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, γ-penta Lactone, pivalolactone, 1,5-dioxepeptan-2-one, 5-(benzyloxy)oxacycloheptan-2-one, 2-bromo-2-methylpropanoic acid 7 - sideoxyoxacycloheptyl-4-yl ester, 5-phenyloxacycloheptan-2-one, 5-methyloxacycloheptan-2-one, 1,4,8-trioxa ( 4,6) spiro-9-undecane, 5-(benzyloxymethyl)oxacycloheptan-2-one, 3-hydroxy-2-(hydroxymethyl)-2-methylpropionic acid 7 - pendant oxetan-4-yl ester, (Z)-6,7-dihydrooxeene-2(3H)-one, glycolide, D-lactide, L- Racemic lactide, 1:1 D:L form lactide and meso-lactide. Also in this embodiment, the cyclic carbonate may be selected from the group consisting of trimethylene carbonate, tetramethylene carbonate, pentamethylene carbonate, 5-methyl-2-sidedoxy- 1,3-Dioxane-5-carboxylic acid, 5-methyl-2-oxo-1,3-dioxan-5-carboxylic acid methyl ester, 5-methyl-2-oxooxy-1 , 3-dioxane-5-carboxylic acid tert-butyl ester, 5-methyl-2-oxo-1,3-dioxane-5-carboxylic acid ethyl ester, 5-methyl-2- side Oxy-1,3-dioxane-5-carbonyl chloride, 5-methyl-2-oxo-1,3-dioxane-5-carboxylic acid benzyl ester, 5-methyl-2- side 2-(tetrahydro-2H-pyran-2-yloxy)ethyl oxy-1,3-dioxane-5-carboxylic acid, 5-methyl-2-oxo-1,3- Dioxane-5-carboxylic acid 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl ester, 5-methyl-2-oxooxy -1,3-dioxane-5-carboxylic acid 2,2,2-trifluoroethyl ester, 5-methyl-2-oxo-1,3-dioxane-5-carboxylic acid prop-2- Alkynyl ester, 5-methyl-2-oxo-1,3-dioxane-5-carboxylic acid allyl ester, 5-methyl-2-oxo-1,3-dioxane- 5-(2-methoxyethoxy)ethyl 5-carboxylate, 5-methyl-2-oxo-1,3-dioxan-5-carboxylic acid 3-(t-butylthio) ) propyl ester, 5-methyl-2- side 2-(t-butoxycarbonylamino)ethyl ester of 5-1,3-dioxane-5-carboxylic acid, 5-methyl-2-oxo-1,3-dioxane-5- 2-(pyridin-2-yldihydrothio)ethyl formate, 4-methyl-2-oxo-1,3-dioxan-5-carboxylic acid 4-(hydroxymethyl)benzyl ester 4-(5-Methyl-2-oxo-1,3-dioxan-5-carbonyloxy)hexahydropyridine-1-carboxylic acid tert-butyl ester, N-benzyl-5-A Benzyl-2-oxo-1,3-dioxan-5-formamide, N-isopropyl-N,5-dimethyl-2-oxo-1,3-dioxane- 5-carbamide, 5,5-dimethyltrimethylene carbonate (5,5-dimethyl-1,3-dioxan-2-one), 5-methyltrimethylene carbonate ( 5-methyl-1,3-dioxan-2-one), 5,5-diethyltrimethylene carbonate (5,5-diethyl-1,3-dioxan-2-one) And 5-ethyl-trimethyl carbonate (5-ethyl-1,3-dioxan-2-one). In another more specific embodiment of the novel block copolymer having structure (1a) or (1b), the ethylenically unsaturated monomer useful for forming polymer block A may comprise a derivative derived from a vinyl aryl monomer. The unit and block B may comprise units derived from an ethylenically unsaturated polymerizable monomer or lactone, and further wherein the block A and B phase phases are separable. In this embodiment, the ethylenically unsaturated polymerizable single system is selected from acrylate or methacrylate, or comprises a ring-opening polymerization (ROP) unit derived from a cyclic carbonate, wherein the vinyl aryl is selected Free group consisting of styrene, 4-methylstyrene and 4-ethylstyrene, and wherein methacrylate, if present, is selected from the group consisting of methyl methacrylate, methacrylic acid Ethyl ester and propyl methacrylate; and the lactone is selected from the group consisting of β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone , γ-valerolactone, pivalolactone, 1,5-dioxepeptan-2-one, 5-(benzyloxy)oxacycloheptan-2-one; selected from trimethylene carbonate , a cyclic carbonate of tetramethylene carbonate, penta methylene carbonate; a glycoside, a 7-oxoxyoxetan-4-yl 2-bromo-2-methylpropionate, 5-benzene Oxecycloheptan-2-one, 5-methyloxacycloheptan-2-one, 1,4,8-trioxa(4,6)spiro-9-undecane, 5-(benzyl Oxymethyl)oxepipene-2-one, 7-oxoxyoxepin-4-yl-3-hydroxy-2-(hydroxymethyl)-2-methylpropanoate (Z)-6,7-dihydrooxetan-2(3H)-one, D-lactide, L-lactide, meso-lactide, and further wherein block A And the B-phase can be separated. The invention also relates to compositions comprising a novel block copolymer of structure (1a) or (1b) and a solvent. Solvents suitable for dissolving the novel block copolymer of structure (1a) or (1b), alone or in combination with other components, include propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, anisole, Ethyl lactate, 2-heptanone, cyclohexanone, amyl acetate, n-butyl acetate, n-amyl ketone (MAK), γ-butyrolactone (GBL), toluene, and the like. Particularly useful casting solvents in the examples include propylene glycol monomethyl ether acetate (PGMEA), gamma-butyrolactone (GBL) or a combination of such solvents. The wt% of the novel block copolymer having the structure (1a) or (1b) in the solvent may be in the range of 0.2 wt% to 10 wt%. In another embodiment, the range can be from 0.5 wt% to 10 wt%. In still another embodiment, the range can be from 0.5 wt% to 5 wt%. In still another more specific embodiment, the range can be from 0.8 wt% to 1.2 wt%. In a particular embodiment, the composition is capable of forming a film layer comprising a block copolymer, wherein the film layer is capable of self-assembly spontaneously and/or during heat treatment, thereby forming a respective chemically distinctly embedded block copolymer comprising The pattern of alternating domains of the phase segregation of the segments. The solution containing the novel block copolymer of structure (1a) or (1b) may further comprise other components and/or additives selected from the group consisting of inorganic-containing polymers; additives, including small molecules, inorganic-containing materials. a molecule, a surfactant, a photoacid generator, a thermal acid generator, a quencher, a hardener, a crosslinker, a chain extender, and the like; and a combination comprising at least one of the foregoing, wherein the other components and/or One or more of the additives or additives are co-assembled with the block copolymer to form a block copolymer assembly. In another aspect of the invention, the novel composition comprising the first block copolymer of structure (1a) or (1b) may further comprise a second different block copolymer of structure (1a) or (1b). In this aspect of the invention, the second block copolymer, which is different from the first block copolymer, may be present from 5 wt% to 50 wt% of the total solids. In another embodiment of the novel composition, the composition comprises a block copolymer of structure (1a) or (1b) and a second block copolymer which does not have a bonding group but comprises a derivative Blocks of ethylenically unsaturated monomers or cyclic monomers as described above for the novel block copolymers. A specific example of a suitable second diblock copolymer containing a high etch resistant block and a highly etchable block may be a block copolymer poly(styrene-b-methyl methacrylate). Generally, block copolymers suitable for use in such inventions have a weight average molecular weight in the range of from about 3,000 g/mol to about 500,000 g/mol (M)._w And a number average molecular weight of about 1,000 to about 60,000 (M)_n And a polydispersity of from about 1.01 to about 6, or from 1.01 to about 2 or from 1.01 to about 1.5 (M)_w /M_n ) (PD). Other specific, non-limiting examples of other diblock copolymers that can be used as other components without a bonding group are poly(styrene-b-methyl methacrylate), poly(styrene-b-butyl) Diene), poly(styrene-b-isoprene), poly(styrene-b-methyl methacrylate), poly(styrene-b-alkenyl aromatic), poly(styrene) -b-(ethylene-propylene)), poly(styrene-b-(t-butyl)-b-(meth)acrylate), poly(styrene-b-tetrahydrofuran), poly(styrene-b-ethylene oxide) ), poly(styrene-b-dimethyloxane), poly(methyl methacrylate-b-dimethyloxane) and poly(methyl methacrylate-b-4-ethylene) Pyridine)). All of the polymeric materials coexist with at least one block having repeating units resistant to the plasma etching techniques typically employed in the fabrication of IC devices and at least one of which is rapidly etched under such conditions or may be removed by chemical or photochemical processes. Block. This allows the guided self-assembled polymer pattern to be transferred to the substrate to affect via formation. In this aspect of the invention, the second block copolymer may be present from 1 wt% to 20 wt% or more preferably from 5 wt% to 10 wt% of the total solids. Another embodiment of this novel composition is one in which it further comprises a homopolymer as another component. The homopolymer may be an ethylenically unsaturated monomer or a cyclic monomer derived from a suitable precursor as previously described as a block of the novel block copolymer of structure (1a) or (1b). A homopolymer of either. The homopolymer component may be present in the composition in an amount ranging from 0.5 wt% to 10 wt% or more specifically from 1 wt% to 5 wt% of the solid. The molar ratio of the novel block copolymer of repeating units in block A to the novel block copolymer of repeating units in block B is between 1.2 and 0.8 and further as set forth above in all of its possible embodiments. The present invention relates to the formation of patterns using novel compositions in a process for guided self-assembly comprising novel block copolymers. Any of the steps of the step of introducing a self-assembling novel block copolymer can be used. The composition comprising the novel block copolymer can be applied to the substrate to form a film by processes such as spin casting, dip coating, doctor blading, spraying, or any other known process. The film of the block copolymer may have a thickness of from 1 nm to 1000 nm and more specifically from 1 nm to 130 nm. Specifically, the film thickness is equal to or greater than 25 nm, specifically, the thickness is in the range of 25 nm to 125 nm. The film may be annealed as appropriate to promote self-assembly and remove defects. Annealing processes include thermal annealing, thermal gradient annealing, solvent vapor annealing, thermal solvent vapor annealing, and the like. Thermal annealing can be carried out at a temperature above the glass transition temperature of the block copolymer and below the thermal decomposition temperature of the block copolymer. Thermal annealing can be carried out at a temperature of from room temperature to about 300 °C. Thermal annealing can be carried out for a period of from about 10 sec to about 100 hours, more specifically from 30 seconds to 1 hour. The block copolymers of the present invention can form self-assembled domains having a variety of morphologies, including flakes, cylinders, and spheres. The size (eg, width) of the domains can range from 1 nm to 100 nm, from 2 nm to 30 nm, or specifically from 3 nm to 20 nm. The invention further relates to a novel process for the novel block copolymers employing structure (1a) or (1b). One of the unexpected results imparted by the novel block copolymer of structure (1a) or (1b) is that when the copolymer is applied to a substrate and subjected to self-assembly, the underlayer need not be non-preferential ( For example, neutral). This is due to the greater latitude of the process for the vertical alignment of the novel block copolymer domains imparted by the presence of surface-active linking groups in structure (1a) or (1b) (with respect to the underlying surface affinity). Another unexpected result imparted by the novel block copolymer of structure (1a) or (1b) is that it provides a significantly thicker block copolymer film than a similar block copolymer without a novel surface active bonding group. The block copolymer domains are vertically aligned with the substrate. In particular, ranges from 25 nm to 125 nm are possible. As a non-limiting example of how this can be used in pattern transfer, when a novel block copolymer is coated onto an underlayer (ie, a substrate) and further processed, the block copolymer forms a cylindrical shape that is oriented perpendicular to the underlying surface. Microphase-separated domains of microdomains. This is because the domains do not have any preference for binding to the underlayer, and this further provides parallel line/space patterns in the block copolymer assembly. The domains so oriented are thermostable under other processing conditions. Thus, after the coating of the novel block copolymer is formed on the underlayer and self-assembled by baking and/or annealing, the domains of the block copolymer will be formed on the surface of the underlayer and remain perpendicular to the underlying surface. One of the domains can be selectively removed in the presence of other domains to generate an etched domain pattern. This selective removal can be achieved by wet or dry processes. In one example, wet or plasma etching can be used with optional UV exposure. Wet etching can utilize acetic acid. A standard plasma etching process can be used, such as a plasma containing oxygen; in addition, argon, carbon monoxide, carbon dioxide, CF can be present in the plasma.₄ , CHF₃ . In the case of thermally decomposable polymer blocks, selective removal can be achieved by thermal baking. In another example, one of the block copolymer domains can be selectively modified after self-assembly to increase its etch resistance. For example, an anti-etching metal or inorganic substance can be introduced from a solution or vapor by chemical infiltration. The domain or functional group can be selectively reacted with a reactive compound such as decane or sulfhydryl chloride. Alternatively, the etching resistant material can be wetted into a domain using a cycle of atomic layer deposition (eg, sequential wetting synthesis). After modification, the less resistant domains can be removed using wet or dry etching processes. After the selective removal process, the resulting etched domain pattern can be further patterned into the substrate layer. The self-assembled block copolymer patterns are transferred to an underlying substrate using known techniques. In some cases, it may be advantageous to reverse the tone of the pattern before transferring into the substrate or after transferring to the layer of the substrate. This can be accomplished by standard tone inversion (eg, backfilling the organic pattern with an anti-etch spin-coating inversion material). Figures 1a and 1b show a schematic depiction of a novel block copolymer of structure (1a) or (1b) and a schematic representation of its self-assembly, respectively. In particular, Figure 1a shows a schematic representation of a novel block copolymer. Figure 1b shows a schematic representation of the block copolymer schematically depicted in Figure 1a when applied to the underlayer (i.e., substrate) that is undergoing two types of self-assembly. In the top view of Figure 1a, the film of block copolymer is oriented to form the domains of vertically oriented sheets. In the bottom view of Figure lb, the domains in the membrane are oriented to form a vertically oriented cylindrical domain. Figures 2a-c show schematic diagrams of guided self-assembly (DSA) of novel block copolymers of structure (1a) or (1b). In particular, Figure 2a shows a patterned epitaxial DSA in which most of the novel block copolymers are confined within the recessed regions of the topographical pre-pattern, the domain of the novel block copolymer subdividing the recessed regions. Figure 2b shows the novel block copolymer coating above and within the shallow periodic topography pre-pattern wherein the domain of the block copolymer is aligned with the topographical pattern. Finally, Figure 2c shows a chemical epitaxial DSA in which the film system of this novel block copolymer is coated over a chemical pre-pattern comprising preferential and non-priority regions (e.g., non-limiting examples of neutral regions), wherein the novel blocks The domains of the copolymer are aligned with the wetting characteristics. Unlike conventional block polymers, the inventive material having the structure (1a) or (1b) of the surface-active bonding group does not require the presence of a substantially non-priority region and thus provides a broad latitude for affinity with respect to the underlying surface. . That is, the novel materials can form domains oriented perpendicular to the substrate during self-assembly for a wide range of underlying surface properties. This may enable a more robust SA performance to be achieved across surfaces having, for example, imperfect or non-uniform surface properties. Imperfect or non-uniform surface properties may be caused by damage to the underlying material, contamination, imperfect deposition/grafting conditions, impurities, poor compositional uniformity, or other causes. Other types of substrates can be used in the above process and in the process of the invention using the novel composition comprising the novel block copolymer of structure (1a) or (1b). As an example, a substrate having a coating of a high carbon underlayer and a ruthenium antireflective coating can be used as the substrate. The high carbon bottom layer can have a coating thickness of from about 20 nm to about 2 microns. An anti-reflective coating of about 10 nm to about 100 nm is applied over the coating. Where a self-assembling cylinder of the novel block copolymer is desired to be oriented perpendicular to the substrate, a neutral layer can be employed. The invention can also be used in a variety of other substrates, such as those prepared by chemical vapor deposition (CVD), physical vapor deposition (PVD), and atomic layer deposition (ALD). The use of such CVD and PVD to prepare substrates is discussed in the following references: "HANDBOOK OF THIN-FILM DEPOSITION PROCESSES AND TECHNIQUES, Principles, Methods, Equipment and Applications, Second Edition, edited by Krishna Seshan, Intel Corporation, Santa Clara, California , Copyright © 2002, Noyes Publications, Library of Congress Catalog Card Number: 2001135178, ISBN: 0-8155-1442-5, Noyes Publications / William Andrew Publishing, 13 Eaton Avenue Norwich, NY 13815, Chapter 1 title: Deposition Technologies and Applications: Introduction and Overview, page 11 - page 43, Chapter 1, the author: Werner Kern and Klaus K. Schuegraf. " The preparation of substrates by ALD is described in the following reference: "Chemical Review 2010, 110, pages 111-131". In another aspect of the invention, a novel composition comprising a block copolymer having structure (1a) or (1b) is used to make first and second layers using a layer of a periodic copolymer having Lo In a method of vertically orienting a block copolymer domain over an unpatterned substrate, the method comprises steps a) and b); wherein a) forming a block copolymer from the novel composition on the unpatterned substrate And b) annealing the layer of the block copolymer to produce a non-zero positive integer number of first and second block copolymer domains oriented vertically on the unpatterned substrate. In this inventive method, the unpatterned substrate may be selected from the group consisting of a polymer brush layer, a crosslinked polymer layer, a self-assembled monolayer, a layer of an anti-reflective coating, by chemical vapor deposition (CVD). Deposited layer, carbon layer, layer deposited by physical vapor deposition (PVD), layer deposited by atomic layer deposition (ALD). In another aspect of the invention, a novel composition comprising a block copolymer having structure (1a) or (1b) is used in a method comprising: using L_O The periodic block copolymer coating causes the first and second block copolymer domains to be vertically oriented above the first patterned substrate (where the height of the pattern topography on the substrate is at least 0.7 times Lo) and the domains In alignment with the pattern, the method comprises steps a) and b); wherein a) utilizing the above mentioned block copolymer comprising structure (1a) or (1b) on the first topography substrate The composition of the novel composition forms a coating of a block copolymer having a bonding group, wherein the average thickness of the block copolymer coating is less than the height of the topography of the first topography substrate, wherein the block copolymer layer is laterally oriented The ground is limited by morphology; and, b) annealing the block copolymer layer to produce first and second block copolymer domains that are vertically oriented to the first patterned substrate and are confined to the recessed region . In this aspect of the invention, the first patterned substrate is formed on the topography forming material above the bottom layer, wherein the topography forming material may be selected from the group consisting of: resist material, crosslinked polymer layer, anti-reflection a layer of a coating, a layer deposited by chemical vapor deposition (CVD), a layer deposited by physical vapor deposition (PVD), a layer deposited by atomic layer deposition (ALD), and further wherein the underlayer is selected from the group consisting of Groups: polymer brush layers, crosslinked polymer layers, self-assembled monolayers, layers of anti-reflective coatings, layers deposited by chemical vapor deposition (CVD), layers deposited by physical vapor deposition (PVD), A layer deposited by atomic layer deposition (ALD). Further, in this aspect of the invention, the resist material may be selected from the group consisting of: an i-line photoresist, a g-line photoresist, a 284 nm photoresist, a 193 nm photoresist, a far ultraviolet light. Resist and electron beam photoresist. Another embodiment is where the antireflective coating material is selected from the group consisting of a bottom anti-reflective coating, a ruthenium anti-reflective coating, and a titanium anti-reflective coating. In another aspect of the invention, a novel composition comprising a block copolymer having structure (1a) or (1b) is used in a method of using a novel coating comprising a block copolymer to have Lo The periodic first and second block copolymer domains have a morphology height greater than 0.7 times Lo and a pitch P₁ (where pitch P₁ A non-zero positive integer multiplied by a topographical pattern of the topographical pattern of the topography of Lo), and the domains are aligned with the pattern, the method comprising steps a) and b); wherein a) is in the second Forming a coating on a patterned substrate from a block copolymer having a surface active bonding group using a composition comprising the novel composition of the block copolymer having the structure (1a) or (1b) as described above, wherein the coating is formed The thickness of the segmented copolymer coating exceeds the height of the topography of the second patterned substrate; and, b) annealing the block copolymer layer to produce a non-zero positive integer number vertically oriented on the second patterned substrate First and second block copolymer domains, and aligning the domains with the second patterned substrate, wherein the sum of the vertically oriented domains is equal to or greater than the pitch P of the topographical pattern₁ . In this aspect of the invention, the first patterned substrate is prepared by treating the topographical organic features on top of the inorganic layer with a plasma that selectively trims the organic features and modifies the exposed surface regions of the inorganic layer. In another aspect of this embodiment, the material having a square appearance on the thin underlayer is selected from the group consisting of: patterned i-line photoresist, g-line photoresist, 248 nm photoresist, 193 Nm photoresist, far ultraviolet photoresist and electron beam photoresist. In the final aspect of this embodiment, the bottom layer can be an anti-reflective coating, or the inorganic layer material can be selected from the group consisting of a ruthenium anti-reflective coating or a titanium anti-reflective coating. In another aspect of the invention, a novel composition comprising a block copolymer having structure (1a) or (1b) is used in a method comprising: using a block comprising a block copolymer having a Lo periodicity a coating of the copolymer such that the first and second block copolymer domains have a pitch P₂ (where pitch P₂ Multi-zero positive integer multiplied by Lo) surface chemical pre-patterned substrate vertically oriented and aligned with the pre-pattern, the method comprising steps a) and b) a) utilizing on a substrate having a surface chemical pre-pattern A novel composition comprising a block copolymer of structure (1a) or (1b) forms a coating of a block copolymer having a surface-active bonding group, b) annealing the block copolymer layer to produce a pitch P₂ The surface chemically pre-patterned substrate is aligned with the vertically oriented first and second block copolymer domains. In this aspect of the invention, the substrate having the surface chemical pre-pattern comprises alternating preferential wetted regions and oriented control regions, wherein the sum of the width of the preferential wetted regions and the width of the oriented control regions is equal to the pre-pattern pitch P₂ Wherein the material used in the oriented control region supports the vertical orientation of the block copolymer domain, and the preferential wetting region has a lower interface to one of the block copolymer domains than the other block copolymer domain energy. In another aspect, a composition comprising a block copolymer having structure (1a) or (1b) is used in a method, the method comprising: providing a first layered structure comprising a top layer (bottom layer); forming a setting a film layer comprising a block copolymer of structure (1a) or (1b) on a bottom layer, wherein the film layer has a top surface in contact with the interface of the atmosphere; and using a heat treatment to induce or induce self-assembly of the block copolymer of the film layer, This forms a second layered structure comprising a phase segregation domain pattern having a characteristic pitch (Lo) comprising a vertically oriented alternating domain comprising respective chemically distinct blocks of the block copolymer. In one embodiment, the domain pattern comprises a flaky domain. In another embodiment, the domain pattern comprises a cylindrical domain. In certain embodiments, the feature pitch (Lo) is from about 4 nm to about 80 nm, from about 4 nm to about 50 nm, or from about 10 nm to about 50 nm. In certain embodiments, the bottom layer is wetted by one of the domains of the self-assembling block copolymer in which all of the fluorine of X is replaced by hydrogen. In certain embodiments, the atmospheric interface is wetted by one of the domains of the self-assembling block copolymer in which all of the fluorine of X is replaced by hydrogen. In certain embodiments, the method also includes selectively etching one of the domains, thereby forming a third comprising an etched domain pattern comprising one or more remaining domains of the self-assembling block copolymer Hierarchical structure. In a particular embodiment, the method includes transferring the etched domain pattern to the substrate. In a particular embodiment, the transfer of the etched domain pattern to the substrate is performed using a tone inversion process relative to the etched domain pattern. In certain embodiments, the induction of self-assembly of the block copolymer of the film layer using heat treatment is comprised between about 80 ° C and about 250 ° C, about 100 ° C and about 250 ° C or about 120 ° C and about 200 ° C. The film layer is baked at a temperature of between about 1 second and about 24 hours, about 10 seconds and about 20 hours or between about 1 minute and about 10 hours. In certain embodiments, the method includes forming a topographic resist pattern disposed on the underlayer prior to the setting of the composition, wherein the film layer comprising the block copolymer for self-assembly is substantially limited to the morphology A recessed area of the resist pattern. In another aspect, a composition comprising a block copolymer having structure (1a) or (1b) is employed in a method, the method comprising: providing a first multilayer structure comprising having a structure for guiding (1a) Or a top surface of the self-assembled pre-pattern of the block copolymer of (1b); forming a film layer comprising a block copolymer disposed on a top surface of the pre-pattern, the film layer comprising a top surface in contact with the atmosphere interface, And the film layer comprises a bottom surface in contact with the top surface of the pre-pattern; and heat treatment is used to induce or induce self-assembly of the block copolymer, thereby forming a second phase segregation domain pattern (domain pattern) comprising the block copolymer A multilayer structure having a pattern disposed on a top surface of the pre-pattern. In certain embodiments, the top surface of the pre-pattern is preferentially wetted by one of the domains of the self-assembled block copolymer wherein all of the fluorine of X is replaced by hydrogen. In some embodiments, the domains are oriented perpendicular to a major plane of the bottom layer of the first multilayer structure. In certain embodiments, the method includes selectively removing one of the domains, thereby forming a third multilayer structure comprising an etched domain pattern, the etched domain pattern comprising the domain pattern One or more remaining domains. In certain embodiments, the method includes transferring the etched domain pattern to one or more underlying layers of the third multilayer structure. In some embodiments, the transfer of the etched domain pattern is performed using a tone inversion process. In some embodiments, the pre-pattern comprises a patterned epitaxial pre-pattern of sidewall features having a sidewall height greater than or equal to the thickness of the film layer, and wherein the film layer is substantially confined to the recessed regions of the pre-pattern. In some embodiments, the pre-pattern comprises a chemical epitaxial pre-pattern having sidewall features that are less than the topographical features of the film thickness, and wherein the film layers are disposed on the topmost and bottommost surfaces of the pre-pattern. The following specific examples will provide a detailed description of the methods of producing and utilizing the compositions of the present invention. However, the examples are not intended to limit or constrain the scope of the invention in any way, and the examples are not to be construed as providing the conditions, parameters or values necessary to practice the invention.Instance Instruments and chemicals The chemicals not specified in Table 1 were obtained from Aldrich Chemical Company (Sigma-Aldrich Corp St. Louis, MO, USA) and used as received. Spin coating and baking of films using the Laurel WS-650-23B spin coater and Tokyo Electron Ltd. Clean Track ACT-8. Nordson (300 Nordson Dr. M/S 47 Amherst, OH 44001 USA unless otherwise indicated) Use of MARCH etching machine for plasma etching without Si domain. AMAT (Applied Materials, Inc. 3050 Bowers Avenue PO Box 58039 Santa Clara, CA 95054-3299 USA) NanoSEM 3D and Hitachi (Hitachi High Technologies America) Inc. 10 North Martingale Road, Suite 500 Schaumburg, Illinois 60173-2295) A top view image and a cross-sectional image are taken on the S-5500. Table 1 gives a list of the abbreviations used for the compounds and solvents used. In this table, "Sigma-Aldrich "Sigma-Aldrich Corporation" at 3050 Spruce St., St. Louis, Missouri 63103; "Synquest" means "SynQuest Laboratories, Inc." at 13201 Rachael Blvd, Rt 2054, "Exfluor" 2350 Double Creek Dr, Round Rock, TX 78664 "Exfluor Research Corporation", "Perstorp Chemicals" means "Pern in Neptunigatan 1, 211 20 Malmö, Sweden" Storp Specialty Chemicals, "Richman Chemicals" means "Richman Chemicals Custom Solutions" at 768 North Bethlehem Pike, PA 19002. The coated SiArc solution (Shin Etsu SHB A-940 L35) is from Shin-Etsu Chemical Co., Ltd. (Tokyo 100-0004, Japan) Commercially available coating solutions AZEMBLY(R) NLD-089, AZEMBLY(R) NLD-208D, AZEMBLY(R) NLD-128 and AZEMBLY(R) NLD-127 were obtained from AZ Electronic Materials (Somerville, NJ).table 1

The acetal protected BISMPA monomer (AcBISMPA) (21) was prepared as previously reported (ACS Macro Letters, 2(1), 19-22; 2013).

(21) Trimethyldecylstyrene (TMSS) (22) was synthesized as previously reported (Macromolecules 2009, 42, 4614-4621).

(twenty two)Instance 1 : Difunctional linear perfluoroalkane utilization ATRP Synthesis of initiator and hydroxy functional groups:

Program 3 About polystyrene bonded by block A (PS) and block B (TMC) via linear perfluoroalkane bonding -b -(linear perfluoroalkane)-poly(trimethyl carbonate) (Scheme 3) synthesis, selective esterification of hexadecafluoro-1,10-decanediol using 2-bromo-2-methylpropionium bromide , as given below:

In a 250 ml round bottom flask equipped with a magnetic stir bar, addition funnel, thermometer and bubble tube, 9.5 g (20.56 mmol) pre-dried 2, 2, 3, 3, 4, 4 under nitrogen. 5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-nonanediol was added to 50 ml of anhydrous DCM. When cooled, 2.23 g (22 mmol) of triethylamine was poured into the flask at 10 °C. Then, 4.6 g (20 mmol) of 2-bromo-2-methylpropionamidine bromide in 30 ml of DCM was added dropwise to the reaction crude at -8 ° C to -3 ° C. The reaction was stirred at room temperature for 20 hours. 150 ml was added to the reaction crude, and then the precipitate was separated by filtration and identified as a salt of TEA·HBr. The mother liquor was evaporated under vacuum. The crude material was analyzed by NMR and GC-MS (Figures 3 and 4). No purification steps were performed at that time. Crude product¹ The results of H NMR and GC-MS indicated the formation of mono- and di-esters with little unreacted diol and TEA·HBr.Instance 2. Sheet forming polystyrene - b -( Linear perfluoroalkane )- Gather ( Lactide lactide ) Morphology of diblock copolymer film The clean surface of the Si substrate was coated with a 51% PS-containing brush-like polymer (AZEMBLYTM NLD-127) by spin coating at 1500 rpm and baked at 250 ° C for 2 min, followed by PGMEA rinse for 30 sec and soft at 110 ° C. Bake for 1 min to process. On the test piece of the surface treated substrate, the modified poly(styrene-b - (linear perfluoroalkane)-lactide (PS-CH)₂ -CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ C ₂ H ₄ -PLA, 11.3k-12.8k, Vf PLA = 0.49,L ₀ 1% of the ~22 nm) PGMEA solution was spin-coated at 3000 rpm and annealed at 110 ° C, 140 ° C and 170 ° C for 5 min in the surrounding atmosphere. A phase separated, vertically oriented lamellae domain is formed on the NLD-127 film which provides a chemically non-preferential surface for the PS and PLA nanodomains at the interface between the bottom layer and the block copolymer film. It was also observed that the growth of the fingerprint grain size in the form of a sheet in a vertical manner was maintained, indicating that the joint modification enhanced the thermal resistance to the morphological perpendicularity of the block copolymer. After the O2 RIE treatment, the corresponding AFM image (Fig. 5) with the perfluoroalkane block copolymer film sample and the SEM image without the bonded modification (Fig. 6) are given below.Comparative example 3 : Sheet-forming polystyrene - b - Gather ( Lactide lactide ) Morphology of diblock copolymer film The clean surface of the Si substrate was coated with a 50% PS-containing brush polymer (AZEMBLYTM NLD-361) by spin coating at 1500 rpm and baked at 250 ° C for 2 min, followed by PGMEA rinse for 30 sec and soft at 110 ° C. Bake for 1 min to process. On the test piece of the surface treated substrate, poly(styrene-b - lactide ()-b -PLA, 8k-9k, Vf PLA = 0.50,L ₀ 1% of the ~19 nm) PGMEA solution was spin-coated at 3000 rpm and annealed at 120 ° C, 140 ° C and 170 ° C for 5 min in the surrounding atmosphere. The phase-separated flaky domains are oriented vertically only by annealing at 120 ° C, while annealing at temperatures above 140 ° C results in the formation of islands/holes, which are typical of parallel sheet morphology. This result indicates that it is used for PS-b The -PLA annealing process is greatly limited in the absence of bonding modification. Corresponding SEM images are given in Figure 6.

Figure 1 a) Schematic representation of the block copolymer of structure (1a) or (1b), and b) schematic representation of a self-assembled, vertically oriented polymer domain. Figure 2 is a schematic depiction of guided self-assembly (DSA) of a novel block copolymer of structure (1a) or (1b): a) shows a patterned epitaxial DSA in which most novel block copolymers are limited in morphology In the recessed region of the pre-pattern, b) a coating of the novel block copolymer above and within the shallow periodic topography pre-pattern, wherein the block copolymer has a domain and a pre-pattern pair Quasi, c) shows a chemical epitaxial DSA in which a film of the novel block copolymer is applied over a chemical pre-pattern comprising preferential and non-priority regions. Figure 3 Reaction of the crude solvent after evaporation 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexafluoro-1,10-癸2 NMR spectrum of FIG. 4 alcoholic solvent evaporated the crude reaction product 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- sixteen-fluoro-1, GC-MS spectrum of FIG. 10- decanediol 5 (a) 110 ℃, (b ) 140 ℃ and (c) annealed at 170 ℃ in the atmosphere around 11k-12k engagement of modified poly (styrene - b AFM height image of the vertically oriented sheet forming block copolymer domain of - lactide. Scale bar = 200 nm. Figure 6 is a phase separation sheet shaped block copolymer of 8k-9k poly(styrene- b -lactide) annealed in ambient atmosphere at (a) 120 ° C, (b) 140 ° C and (c) 170 ° C. SEM image of the domain. Scale bar = 200 nm.

Claims (56)

A block copolymer comprising: a first polymer block (block A); a second polymer block (block B) having a chemical structure different from block A and capable of self-blocking A phase Segregation; and a divalent linking group X covalently linking the terminal repeating unit of block A to the terminal repeating unit of block B, wherein X contains 1-24 fluorines, wherein each of the fluorines of X Linked to the framework carbon of the block copolymer. The block copolymer of claim 1, wherein the film layer comprising the block copolymer is capable of self-assembly spontaneously and/or during heat treatment, thereby forming a respective chemically distinct block comprising the block copolymer. The pattern of alternating domains of phase segregation. The block copolymer of claim 1, wherein the block A comprises an olefinic repeating unit of the formula (A-1): (A-1), wherein i) R ^w is a monovalent group selected from the group consisting of H, F, methyl, ethyl and trifluoromethyl (*-CF3), and ii) R ^d contains A monovalent group linked to the aromatic ring of carbon 1. The block copolymer of claim 1, wherein X has a surface energy lower than block A and a surface energy lower than block B. The block copolymer of claim 1 wherein X has a surface energy between 0 mN/m and 30 mN/m. The block copolymer of claim 1, wherein X comprises a fluorinated alkyl group of formula (C-1): (C-1), wherein each carbon linked to fluorine is a skeleton carbon of the block copolymer, n' is an integer having a value of 2-12, m' is an integer having a value of 1-5, and k 'An integer having a value of 1-5. The block copolymer of claim 1, wherein X comprises a divalent linear fluorinated oxirane group of formula (C-2): (C-2), wherein each carbon linked to fluorine is a skeleton carbon of the block copolymer, and n'' is an integer having a value of 1-5. The block copolymer of claim 1, wherein the block B comprises an aliphatic carbonate repeating unit. The block copolymer of claim 8, wherein the aliphatic carbonate repeating unit comprises a pendant ester group. The block copolymer of claim 9, wherein the aliphatic carbonate repeating unit has the structure of formula (B-4): (B-4), wherein R ^g is a monovalent hydrocarbon group containing 1 to 20 carbons. The block copolymer of claim 10, wherein R ^g is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl and benzyl. The block copolymer of claim 1, wherein the block B comprises an aliphatic ester repeating unit. The block copolymer of claim 12, wherein the aliphatic ester repeating unit has a structure selected from the group consisting of: Where j' is an integer having a value of 0-4, and . The block copolymer of claim 1 wherein block B comprises an aliphatic ether repeating unit. The block copolymer of claim 14, wherein the aliphatic ether repeating unit is selected from the group consisting of ethylene oxide, propylene oxide, ring-opening glycidyl ether, and combinations thereof. The block copolymer of claim 1, wherein the block A comprises an olefinic repeating unit selected from the group consisting of: And their combinations. The block copolymer of claim 1, wherein the block B comprises a homopolymer of a repeating unit selected from the group consisting of . A composition comprising: a solvent; and the block copolymer of claim 1; wherein the composition is capable of forming a film layer comprising the block copolymer, wherein the film layer is capable of spontaneously and/or during heat treatment Assembly, thereby forming a pattern of alternating domains comprising phase segregation of the respective chemically distinct blocks of the block copolymer. A method comprising: providing a first layered structure comprising a top layer (bottom layer); forming a film layer comprising the block copolymer of claim 1 disposed on the bottom layer, wherein the film layer has an interface with the atmosphere a top surface; and a heat treatment to induce or induce self-assembly of the block copolymer of the film layer, thereby forming a second layered structure comprising a phase segregation domain pattern having a characteristic pitch (Lo), the domain pattern A vertically oriented alternating domain comprising the respective chemically distinct blocks of the block copolymer is included. The method of claim 19, wherein the domain pattern comprises a flaky domain. The method of claim 19, wherein the domain pattern comprises a cylindrical domain. The method of claim 19, wherein the characteristic pitch (Lo) is from about 4 nm to about 80 nm. The method of claim 19, wherein the underlayer is preferentially wetted by one of the domains of the self-assembled block copolymer wherein all of the fluorine of X is replaced by hydrogen. The method of claim 19, wherein the atmospheric interface is preferentially wetted by one of the domains of the self-assembled block copolymer wherein all of the fluorine of X is replaced by hydrogen. The method of claim 19, comprising selectively etching one of the domains, thereby forming a third comprising an etched domain pattern comprising one or more of the remaining domains of the self-assembling block copolymer Hierarchical structure. The method of claim 25, comprising transferring the etched domain pattern to the substrate. The method of claim 26, wherein the transfer of the etched domain pattern to the substrate is performed using a tone inversion process relative to the etched domain pattern. The method of claim 19, wherein the inducing the self-assembly of the block copolymer of the film layer by heat treatment comprises baking the film layer at a temperature between about 80 ° C and about 250 ° C for about 1 second and about Between 24 hours. The method of claim 19, wherein the method comprises forming a topographic resist pattern disposed on the underlayer prior to the setting of the composition of claim 15 comprising the block copolymer for self-assembly The film layer is substantially confined to the recessed regions of the topographical resist pattern. A method comprising: providing a first multilayer structure comprising a top surface having a pre-pattern for directing self-assembly of the block copolymer of claim 1; forming the top surface disposed on the pre-pattern comprising the a film layer of a block copolymer, the film layer comprising a top surface in contact with the interface of the atmosphere, and the film layer comprising a bottom surface in contact with the top surface of the pre-pattern; and using a heat treatment to induce or induce the block copolymer Assembly, thereby forming a second multilayer structure comprising a phase segregation domain pattern (domain pattern) of the block copolymer, the domain pattern being disposed on the top surface of the pre-pattern. The method of claim 30, wherein the top surface of the pre-pattern is preferentially wetted by one of the domains of the self-assembled block copolymer wherein all of the fluorine of X is replaced by hydrogen, and the structures The domains are oriented perpendicular to the major plane of the bottom layer of the first multilayer structure. The method of claim 30, comprising selectively removing one of the domains, thereby forming a third multilayer structure comprising the etched domain pattern, the etched domain pattern comprising the domain pattern One or more remaining domains. The method of claim 32, comprising transferring the etched domain pattern to one or more underlying layers of the third multilayer structure. The method of claim 32, wherein the transition of the etched domain pattern is performed using a tone inversion method. The method of claim 30, wherein the pre-pattern comprises a patterned epitaxial pre-pattern having a sidewall height greater than or equal to a topographical feature of the film thickness, and wherein the film layer is substantially confined to the recessed region of the pre-pattern. The method of claim 30, wherein the pre-pattern comprises a chemical epitaxial pre-pattern having a sidewall height less than a topographical feature of the film thickness, and wherein the film layer is disposed on the topmost and bottommost surfaces of the pre-pattern. a diblock copolymer of the formula (1b), (1b) wherein E ¹ is a monovalent first terminal group, E ² is a monovalent second terminal group, and P′ represents a first polymer chain of the first block (block A) of the block copolymer, P'' represents the second polymer chain of the second block (block B) of the block copolymer, and X is a bivalent link linking the terminal repeating unit of P' to the terminal repeating unit of P'' a group wherein X contains 1-24 fluorines, and each of the fluorines of X is linked to the backbone carbon of the block copolymer. The block copolymer of claim 37, wherein the first block comprises a copolymer of styrene and trimethyldecyl styrene. The block copolymer of claim 37, wherein X has the following structure Where n' is an integer having a value from 1-12. The block copolymer of claim 37, wherein X has the following structure , where n'' is an integer having a value of 1-5. a block copolymer having a bonding group having the structure (1a), (1a) wherein, the A-block polymer chain, the B-block polymer chain, wherein the A and B are chemically different covalently linked to the polymer chain, the mesophase is separable; the X system is polymerized in the A a divalent linking group between the block and the B polymer block, selected from the group consisting of a fluorine-containing portion, a portion containing Si ₁ -Si ₈ decane, a hydrocarbon having at least 18 carbons Part and combinations thereof, and further wherein X has a surface energy less than block A and less than the block B. The block copolymer of claim 41, wherein (i) the polymer chain of block A comprises a unit derived from an ethylenically unsaturated polymerizable monomer or a ring-opening polymerization (ROP) derived from a cyclic monomer. a unit of (ii) block B comprising a unit derived from an ethylenically unsaturated polymerizable monomer or a ring-opening polymerization (ROP) derived from a cyclic monomer, and further wherein the polymer is embedded Segments A and B are chemically distinct and the phases are separable. The block copolymer of claim 41, wherein X is selected from the group consisting of fluorine-containing moieties consisting of fluorine-containing linear hydrocarbon groups, fluorine-containing branched hydrocarbon groups, and fluorine-containing linear alkyl ether groups. a group, a fluorine-containing branched alkyl ether group, and a mixture thereof. The block copolymer of claim 41, wherein the X is selected from the group consisting of Si ₁ -Si ₈ oxane, a Si ₁ -Si ₈ oxane moiety, a carbon decane, a decene, and a mixture thereof. . The block copolymer of claim 41, wherein X is selected from the group consisting of hydrocarbons having at least 18 carbons: a linear hydrocarbon group having at least 18 carbons and a branched hydrocarbon having at least 18 carbons . The block copolymer of claim 41, wherein X is selected from the group consisting of fluorine-containing hydrocarbon groups consisting of linear C ₁ -C ₁₀ fluoroalkylene, C ₃ -C ₁₀ branched fluoroalkylene, Alkylfluoroalkyl (-(CH ₂ ) _q (CF ₂ ) _r -CF ₂ -), CFH-containing alkyl fluoroalkyl (-(-CH _2- ) _q (CHF) _q2 (CF ₂ ) _r -CF ₂ -), alkyl fluoroether-fluoroalkyl-(-CH _2- ) _q (-CF ₂ -O-) _s (-CF ₂ CF ₂ -O-) _t (CF ₂ ) _u CF ₂ -, the alkylene group containing CHF desflurane - fluoro alkylene group _{(-CH 2-) q (CHF)} q2 (-CF 2 -O-) s (-CF 2 CF 2 -O-) t (CF ₂ ) _u CF ₂ - and part with structure (2) (2) where q is an integer from 0 to 10, q2 is an integer from 1 to 10, r is an integer from 1 to 10, s is an integer from 0 to 10, t is an integer from 1 to 10, and u is between 0 and An integer between 10, x is 1 to 5, y is 1 to 5, and P is a direct bond, a C ₁ to C ₄ alkyl group or a -CH ₂ -CH ₂ -(CF ₂ ) ₄ - moiety. The block copolymer of claim 41, wherein X has a surface energy of less than about 30 mN m ^-1 . A composition comprising the block copolymer of claim 41 and a solvent. The composition of claim 48, which further comprises another block copolymer. The composition of claim 48, which further comprises a homopolymer. A method of vertically orienting first and second block copolymer domains over an unpatterned substrate using a layer of Lo periodic block copolymer comprising the steps of: a) on the unpatterned substrate Forming a coating of a block copolymer having a bonding group using the composition of claim 48; and, b) annealing the layer of the block copolymer to produce a non-zero orientation vertically oriented on the unpatterned substrate A positive integer number of first and second block copolymer domains. A method of vertically orienting first and second block copolymer domains on a first patterned substrate and aligning the domains with the pattern using a coating comprising a block copolymer having a periodicity of Lo, Wherein the pattern has a topography height of at least 0.7 times Lo, the method comprising the steps of: a) forming the block copolymer having a bonding group on the first topography substrate using the composition of claim 48; The coating of the article, wherein the thickness of the average thickness of the coating of the block copolymer is less than the height of the topography of the first topography substrate, wherein the side of the block copolymer layer is restricted upward by the topography; b) annealing the block copolymer layer to produce first and second block copolymer domains that are vertically oriented on the first patterned substrate and are confined within the recessed regions. One kind of the vertical orientation of the first and second block copolymer having a domain in the Lo periodic topography having a height and having a pitch P Lo is greater than 0.7 times the topography of _a pattern of the second substrate and patterned over the Alignment with other domains of the pattern, wherein the pitch P ₁ is multiplied by the Lo-based non-zero positive integer, the method comprising the steps of: a) using a composition of 48 items as requested on the second patterned substrate Forming a coating of the block copolymer having a surface active bonding group, wherein a thickness of the coating of the block copolymer is greater than a height of the topography of the second patterned substrate; and, b) The segment of the copolymer layer is annealed to produce a non-zero positive integer number of first and second block copolymer domains oriented vertically on the second patterned substrate, and the domains are aligned with the second patterned substrate The sum of the vertically oriented domains is equal to or greater than the pitch P _{1 of} the topographical pattern. One kind of the first and second block copolymer domain vertically oriented and the method of such domains aligned over a substrate having a surface having a pitch P ₂ of the chemical pre-pattern, wherein the pitch P ₂ based nonzero Multiplying a positive integer by Lo, the method comprising the steps of: a) forming a coating of the block copolymer having a surface-active bonding group using the composition of claim 48 on the substrate having a surface chemical pre-pattern; , b) so that the block copolymer layer having a vertical annealing to produce a first and a second block copolymer domain orientation of the substrate having the aligning pitch P ₂ of the surface of the chemical pre-pattern. a block copolymer having the following structure Wherein n ́ ́ ́ is an integer having a value of 1-12, and m ́ ́ ́ is an integer having a value of 1-10. a block copolymer having the following structure Wherein n ́ ́ ́ is an integer having a value of 1-12, and m ́ ́ ́ is an integer having a value of 1-10.