JP2023179038A - Film-forming composition and method of manufacturing semiconductor substrate - Google Patents
Film-forming composition and method of manufacturing semiconductor substrate Download PDFInfo
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- JP2023179038A JP2023179038A JP2022092076A JP2022092076A JP2023179038A JP 2023179038 A JP2023179038 A JP 2023179038A JP 2022092076 A JP2022092076 A JP 2022092076A JP 2022092076 A JP2022092076 A JP 2022092076A JP 2023179038 A JP2023179038 A JP 2023179038A
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- 239000000758 substrate Substances 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 239000004065 semiconductor Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 125000003118 aryl group Chemical group 0.000 claims abstract description 100
- 150000001875 compounds Chemical class 0.000 claims abstract description 80
- 229920000642 polymer Polymers 0.000 claims abstract description 67
- 239000002904 solvent Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000000137 annealing Methods 0.000 claims abstract description 27
- 238000005468 ion implantation Methods 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 229920005989 resin Polymers 0.000 claims description 25
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- 125000000962 organic group Chemical group 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
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Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
本発明は、膜形成用組成物及び半導体基板の製造方法に関する。 The present invention relates to a film-forming composition and a method for manufacturing a semiconductor substrate.
次世代の小型、低損失、かつ、高出力のパワー半導体材料として、炭化ケイ素（ＳｉＣ）や窒化ガリウム（ＧａＮ）などのワイドバンドギャップ半導体が注目されている。ＳｉＣ等に対する不純物の拡散係数は極めて小さいことから、一般的にイオン注入とこれに続いて不純物を活性化するための高温アニーリングとを行う。 Wide bandgap semiconductors such as silicon carbide (SiC) and gallium nitride (GaN) are attracting attention as next-generation compact, low-loss, and high-output power semiconductor materials. Since the diffusion coefficient of impurities in SiC and the like is extremely small, ion implantation is generally followed by high-temperature annealing to activate the impurities.
高温アニーリングの際、ＳｉＣ表面からＳｉが脱離したり、表面原子を再配列したりして基板表面に数ｎｍ程度の荒れが生じ、半導体デバイスのゲート絶縁膜の信頼性やチャネル移動度が低下する場合がある。そこで、表面に保護膜を設けて高温処理するキャップアニーリング技術が提案されている（特許第６３４８８０１号公報）。 During high-temperature annealing, Si is desorbed from the SiC surface and surface atoms are rearranged, resulting in roughness of several nanometers on the substrate surface, which reduces the reliability of the gate insulating film and channel mobility of semiconductor devices. There are cases. Therefore, a cap annealing technique has been proposed in which a protective film is provided on the surface and high temperature treatment is performed (Japanese Patent No. 6348801).
半導体材料の高品質化には、キャップアニーリングの際の表面の荒れをサブナノメートルオーダーで抑制して高平坦性の基板表面とすることが要求される。 In order to improve the quality of semiconductor materials, it is necessary to suppress surface roughness during cap annealing to the subnanometer order to obtain a highly flat substrate surface.
本発明は以上のような事情に基づいてなされたものであり、その目的は、高温アニーリングの際に高平坦性を基板表面に付与し得るキャッピング膜を形成可能な膜形成用組成物及びこれを用いる半導体基板の製造方法を提供することにある。 The present invention has been made based on the above circumstances, and its object is to provide a film-forming composition capable of forming a capping film that can impart high flatness to a substrate surface during high-temperature annealing, and a film-forming composition using the same. An object of the present invention is to provide a method for manufacturing a semiconductor substrate used in the present invention.
本発明は、一実施形態において、
半導体基板の製造において、基板へのイオン注入工程後のアニーリング工程におけるキャッピング膜を形成するための膜形成用組成物であって、
芳香環を有する化合物（以下、「［Ａ］化合物」ともいう。）と、
溶媒（以下、「［Ｂ］溶媒」ともいう。）と
を含み、
上記芳香環を有する化合物が、主鎖に芳香環を有する重合体（以下、「［Ａ１］重合体」ともいう。）、分子量が６００以上３０００以下の芳香環含有化合物（以下、「［Ａ２］芳香環含有化合物」ともいう。）又はこれらの組み合わせである、膜形成用組成物に関する。
In one embodiment, the present invention provides:
A film-forming composition for forming a capping film in an annealing step after an ion implantation step into a substrate in the production of a semiconductor substrate, the composition comprising:
A compound having an aromatic ring (hereinafter also referred to as "[A] compound"),
A solvent (hereinafter also referred to as "[B] solvent");
The compound having an aromatic ring is a polymer having an aromatic ring in the main chain (hereinafter also referred to as "[A1] polymer"), an aromatic ring-containing compound having a molecular weight of 600 or more and 3000 or less (hereinafter referred to as "[A2] (also referred to as "aromatic ring-containing compound") or a combination thereof.
本発明は、他の実施形態において、
基板にイオン注入する工程と、
上記イオン注入工程後の上記基板の少なくともイオン注入領域に膜形成用組成物を塗工する工程と、
上記膜形成用組成物塗工工程により形成されたキャッピング膜を有する基板を１０００℃以上でアニーリングする工程と
を備え、
上記膜形成用組成物が、
芳香環を有する化合物と、
溶媒と
を含み、
上記芳香環を有する化合物が、主鎖に芳香環を有する樹脂、分子量が６００以上３０００以下の芳香環含有化合物又はこれらの組み合わせである、半導体基板の製造方法に関する。
In other embodiments, the present invention provides:
A step of implanting ions into the substrate,
a step of applying a film-forming composition to at least the ion-implanted region of the substrate after the ion-implanting step;
a step of annealing the substrate having the capping film formed by the film-forming composition coating step at 1000° C. or higher;
The film-forming composition described above is
A compound having an aromatic ring,
containing a solvent and
The present invention relates to a method for manufacturing a semiconductor substrate, wherein the compound having an aromatic ring is a resin having an aromatic ring in its main chain, an aromatic ring-containing compound having a molecular weight of 600 or more and 3000 or less, or a combination thereof.
当該膜形成用組成物によれば、高温アニーリングの際に高平坦性を基板表面に付与し得るキャッピング膜を効率的に形成することができる。当該半導体基板の製造方法によれば、高温アニーリングの際に高平坦性を基板表面に付与し得るキャッピング膜を形成するため、高品質の半導体基板を提供することができる。従って、これらは、今後さらに高機能化が進行すると予想される半導体デバイスの製造等に好適に用いることができる。 According to the film-forming composition, a capping film that can impart high flatness to the substrate surface during high-temperature annealing can be efficiently formed. According to the method for manufacturing a semiconductor substrate, a capping film that can impart high flatness to the substrate surface during high-temperature annealing is formed, so a high-quality semiconductor substrate can be provided. Therefore, these can be suitably used in the production of semiconductor devices, which are expected to become more sophisticated in the future.
以下、本発明の各実施形態に係る膜形成用組成物及び半導体基板の製造方法について詳説する。実施形態における好適な態様の組み合わせもまた好ましい。 Hereinafter, a film-forming composition and a method for manufacturing a semiconductor substrate according to each embodiment of the present invention will be explained in detail. Combinations of preferred aspects in the embodiments are also preferred.
《膜形成用組成物》
当該膜形成用組成物（以下、単に「組成物」ともいう。）は、半導体基板の製造において、基板へのイオン注入工程後のアニーリング工程におけるキャッピング膜を形成するために用いられ、［Ａ］化合物と［Ｂ］溶媒とを含有する。当該組成物は、本発明の効果を損なわない範囲において、任意成分を含有していてもよい。
《Film-forming composition》
The film-forming composition (hereinafter also simply referred to as "composition") is used to form a capping film in the annealing process after the ion implantation process into the substrate in the manufacture of semiconductor substrates, and [A] Contains a compound and a [B] solvent. The composition may contain optional components within a range that does not impair the effects of the present invention.
以下、当該組成物が含有する各成分について説明する。 Each component contained in the composition will be explained below.
＜［Ａ］化合物＞
［Ａ］化合物は、芳香環を有する化合物であり、［Ａ１］重合体、［Ａ２］芳香環含有化合物（ただし、［Ａ１］重合体に該当する化合物を除く。）又はこれらの組み合わせである。［Ａ１］重合体及び［Ａ２］芳香環含有化合物はそれぞれ１種単独で又は２種以上を組み合わせて用いることができる。
<[A] Compound>
[A] Compound is a compound having an aromatic ring, and is a [A1] polymer, [A2] aromatic ring-containing compound (excluding compounds corresponding to [A1] polymer), or a combination thereof. [A1] The polymer and [A2] the aromatic ring-containing compound can each be used singly or in combination of two or more.
上記芳香環としては、環員数５～４０の芳香環が好ましく、環員数９～４０の多環縮合芳香環が好ましい。上記芳香環としては、例えばベンゼン環、ナフタレン環、アントラセン環、フェナレン環、フェナントレン環、ピレン環、フルオレン環、ペリレン環、コロネン環等の芳香族炭化水素環、フラン環、ピロール環、チオフェン環、ホスホール環、ピラゾール環、オキサゾール環、イソオキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、トリアジン環等の複素芳香環、又はこれらの組み合わせ等が挙げられる。上記芳香環は、ベンゼン環、ナフタレン環、アントラセン環、フェナレン環、フェナントレン環、ピレン環、フルオレン環及びペリレン環からなる群より選ばれる少なくとも１つの芳香族炭化水素環であることが好ましい。 The aromatic ring is preferably an aromatic ring having 5 to 40 ring members, and preferably a polycyclic condensed aromatic ring having 9 to 40 ring members. Examples of the aromatic rings include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, phenalene ring, phenanthrene ring, pyrene ring, fluorene ring, perylene ring, coronene ring, furan ring, pyrrole ring, thiophene ring, Examples include heteroaromatic rings such as a phosphole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring, or combinations thereof. The aromatic ring is preferably at least one aromatic hydrocarbon ring selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a phenalene ring, a phenanthrene ring, a pyrene ring, a fluorene ring, and a perylene ring.
本明細書において、「環員数」とは、環を構成する原子の数をいう。例えば、ビフェニル環の環員数は１２であり、ナフタレン環の環員数は１０であり、フルオレン環の環員数は１３である。「多環縮合芳香環」とは、複数の芳香環が辺（隣接する２つの炭素原子間の結合）を共有する形で構成された多環性の芳香族炭化水素をいう。 As used herein, "number of ring members" refers to the number of atoms constituting the ring. For example, the biphenyl ring has 12 ring members, the naphthalene ring has 10 ring members, and the fluorene ring has 13 ring members. The term "polycyclic fused aromatic ring" refers to a polycyclic aromatic hydrocarbon composed of a plurality of aromatic rings sharing edges (bonds between two adjacent carbon atoms).
［Ａ］化合物は、耐熱性の点で、ドーパントを含まないことが好ましい。 From the viewpoint of heat resistance, the [A] compound preferably does not contain a dopant.
（［Ａ１］重合体）
［Ａ１］重合体は、主鎖に芳香環を有する重合体である。主鎖に含まれる芳香環としては、上記環員数５～４０の芳香環を好適に採用することができる。上記主鎖に芳香環を有する樹脂としては、耐熱性の観点から、重縮合化合物が好ましい。
([A1] Polymer)
[A1] The polymer is a polymer having an aromatic ring in the main chain. As the aromatic ring contained in the main chain, the above-mentioned aromatic ring having 5 to 40 ring members can be suitably employed. The resin having an aromatic ring in the main chain is preferably a polycondensation compound from the viewpoint of heat resistance.
［Ａ］化合物としての［Ａ１］重合体は、下記式（１）で表される繰り返し単位を有する重合体（以下、「［Ａ１１］重合体」ともいう。）であることが好ましい。［Ａ１１］重合体は、下記式（１）で表される繰り返し単位を２種以上有していてもよい。
上記式（１）中、Ａｒ１における環員数５～４０の芳香環としては、上記環員数５～４０の芳香環を好適に採用することができる。中でも、Ａｒ１の芳香環としては、ベンゼン環、ナフタレン環、ピレン環、フルオレン環又はこれらの組み合わせであることが好ましい。 In the above formula (1), the aromatic ring having 5 to 40 ring members described above can be suitably employed as the aromatic ring having 5 to 40 ring members in Ar 1 . Among these, the aromatic ring of Ar 1 is preferably a benzene ring, a naphthalene ring, a pyrene ring, a fluorene ring, or a combination thereof.
上記式（１）中、Ａｒ１で表される環員数５～４０の芳香環を有する２価の基としては、上記Ａｒ１における環員数５～４０の芳香環又は当該芳香環と鎖状構造との組み合わせから２個の水素原子を除いた基等が好適に挙げられる。芳香環を組み合わせる場合、芳香環同士は縮合環構造のほか、単結合で結合していてもよい。 In the above formula (1), the divalent group having an aromatic ring with 5 to 40 ring members represented by Ar 1 is an aromatic ring with 5 to 40 ring members in Ar 1 or a chain structure with the aromatic ring. Preferred examples include groups obtained by removing two hydrogen atoms from the combination with . When aromatic rings are combined, the aromatic rings may be bonded together through a fused ring structure or a single bond.
鎖状構造としては、炭素数１～２０の鎖状炭化水素を好適に採用することができる。炭素数１～２０の２価の鎖状炭化水素としては、例えば、メタン、エタン、プロパン、ブタン、ヘキサン、オクタン等が挙げられる。これらは直鎖状又は分岐状のいずれであってもよい。中でも、炭素数１～８の直鎖状又は分岐状のアルカンが好ましい。 As the chain structure, a chain hydrocarbon having 1 to 20 carbon atoms can be preferably used. Examples of divalent chain hydrocarbons having 1 to 20 carbon atoms include methane, ethane, propane, butane, hexane, and octane. These may be linear or branched. Among these, linear or branched alkanes having 1 to 8 carbon atoms are preferred.
上記式（１）中、Ｒ０及びＲ１で表される炭素数１～４０の１価の有機基としては、例えば、炭素数１～２０の１価の炭化水素基、この炭化水素基の炭素－炭素間若しくは炭素鎖末端に２価のヘテロ原子含有基を有する基、上記炭化水素基が有する水素原子の一部又は全部を１価のヘテロ原子含有基で置換した基又はこれらの組み合わせ等があげられる。 In the above formula (1), the monovalent organic group having 1 to 40 carbon atoms represented by R 0 and R 1 is, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms; A group having a divalent heteroatom-containing group between carbons or at the end of a carbon chain, a group in which part or all of the hydrogen atoms of the above hydrocarbon group are replaced with a monovalent heteroatom-containing group, or a combination thereof, etc. can be given.
炭素数１～２０の１価の炭化水素基としては、例えば、炭素数１～２０の１価の鎖状炭化水素基、炭素数３～２０の１価の脂環式炭化水素基、炭素数６～２０の１価の芳香族炭化水素基又はこれらの組み合わせ等があげられる。 Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. Examples include 6 to 20 monovalent aromatic hydrocarbon groups or combinations thereof.
本明細書において、「炭化水素基」には、鎖状炭化水素基、脂環式炭化水素基及び芳香族炭化水素基が含まれる。この「炭化水素基」には、飽和炭化水素基及び不飽和炭化水素基が含まれる。「鎖状炭化水素基」とは、環構造を含まず、鎖状構造のみで構成された炭化水素基を意味し、直鎖状炭化水素基及び分岐鎖状炭化水素基の両方を含む。「脂環式炭化水素基」とは、環構造としては脂環構造のみを含み、芳香環構造を含まない炭化水素基を意味し、単環の脂環式炭化水素基及び多環の脂環式炭化水素基の両方を含む（ただし、脂環構造のみで構成されている必要はなく、その一部に鎖状構造を含んでいてもよい）。「芳香族炭化水素基」とは、環構造として芳香環構造を含む炭化水素基を意味する（ただし、芳香環構造のみで構成されている必要はなく、その一部に脂環構造や鎖状構造を含んでいてもよい）。 In this specification, the "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. This "hydrocarbon group" includes a saturated hydrocarbon group and an unsaturated hydrocarbon group. The term "chain hydrocarbon group" refers to a hydrocarbon group that does not contain a ring structure and is composed only of a chain structure, and includes both linear hydrocarbon groups and branched hydrocarbon groups. "Alicyclic hydrocarbon group" means a hydrocarbon group that contains only an alicyclic structure as a ring structure and does not contain an aromatic ring structure, and includes monocyclic alicyclic hydrocarbon groups and polycyclic alicyclic hydrocarbon groups. (However, it does not need to be composed only of an alicyclic structure, and may include a chain structure as part of it.) "Aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure (however, it does not need to be composed only of an aromatic ring structure, and some of it may have an alicyclic structure or a chain structure). structure).
炭素数１～２０の１価の鎖状炭化水素基としては、例えばメチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等のアルキル基；エテニル基、プロペニル基、ブテニル基等のアルケニル基；エチニル基、プロピニル基、ブチニル基等のアルキニル基などが挙げられる。 Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, etc. Alkyl groups; alkenyl groups such as ethenyl, propenyl and butenyl; alkynyl groups such as ethynyl, propynyl and butynyl; and the like.
炭素数３～２０の１価の脂環式炭化水素基としては、例えばシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基；シクロプロペニル基、シクロペンテニル基、シクロヘキセニル基等のシクロアルケニル基；ノルボルニル基、アダマンチル基、トリシクロデシル基等の橋かけ環飽和炭化水素基；ノルボルネニル基、トリシクロデセニル基等の橋かけ環不飽和炭化水素基などが挙げられる。 Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; cyclopropenyl, cyclopentenyl, and cyclohexenyl; Examples include cycloalkenyl groups; bridged ring saturated hydrocarbon groups such as norbornyl, adamantyl, and tricyclodecyl groups; bridged ring unsaturated hydrocarbon groups such as norbornenyl and tricyclodecenyl groups.
炭素数６～２０の１価の芳香族炭化水素基としては、フェニル基、トリル基、ナフチル基、アントラセニル基、ピレニル基等が挙げられる。 Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, tolyl group, naphthyl group, anthracenyl group, and pyrenyl group.
２価又は１価のヘテロ原子含有基を構成するヘテロ原子としては、例えば、酸素原子、窒素原子、硫黄原子、リン原子、ケイ素原子、ハロゲン原子等があげられる。ハロゲン原子としては、例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子があげられる。 Examples of the heteroatom constituting the divalent or monovalent heteroatom-containing group include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a halogen atom, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
２価のヘテロ原子含有基としては、例えば、－ＣＯ－、－ＣＳ－、－ＮＨ－、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、又はこれらを組み合わせた基等があげられる。 Examples of the divalent heteroatom-containing group include -CO-, -CS-, -NH-, -O-, -S-, -SO-, -SO 2 -, or a combination thereof. It will be done.
１価のヘテロ原子含有基としては、例えば、ヒドロキシ基、スルファニル基、シアノ基、ニトロ基、ハロゲン原子等があげられる。 Examples of the monovalent heteroatom-containing group include a hydroxy group, a sulfanyl group, a cyano group, a nitro group, and a halogen atom.
上記Ｒ０は水素原子であることが好ましい。 The above R 0 is preferably a hydrogen atom.
［Ａ］化合物としての［Ａ１］重合体は、ヒドロキシ基、下記式（２－１）で表される基及び下記式（２－２）で表される基からなる群より選ばれる少なくとも１つの基（以下、下記式（２－１）で表される基又は下記式（２－２）で表される基を「基（α）」ともいう。）を有することが好ましい。
上記式（２－１）及び（２－２）中、Ｒ７で表される炭素数１～２０の２価の有機基としては、上記式（１）のＲ０及びＲ１で表される炭素数１～４０の１価の有機基のうち炭素数１～２０に対応する構造から水素原子を１個除いた基を好適に採用することができる。 In the above formulas (2-1) and (2-2), the divalent organic group having 1 to 20 carbon atoms represented by R 7 is represented by R 0 and R 1 in the above formula (1). Among monovalent organic groups having 1 to 40 carbon atoms, a group obtained by removing one hydrogen atom from a structure corresponding to 1 to 20 carbon atoms can be suitably employed.
Ｒ７としてはメタンジイル基、エタンジイル基、フェニレン基等の炭素数１～１０の２価の炭化水素基、－Ｏ－又はこれらの組み合わせが好ましく、メタンジイル基、又はメタンジイル基と－Ｏ－との組み合わせがより好ましい。 R 7 is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms such as a methanediyl group, an ethanediyl group, or a phenylene group, -O-, or a combination thereof; a methanediyl group or a combination of a methanediyl group and -O- is more preferable.
［Ａ］化合物としての［Ａ１］重合体は、上記式（２－１）で表される基を有し、該基は下記式（２－１－１）で表されることが好ましい。
上記式（１）のＡｒ１、Ｒ０及びＲ１のうちの少なくとも１つは、ヒドロキシ基又は上記基（α）を有することが好ましい。少なくともＡｒ１がヒドロキシ基又は基（α）を有することが好ましい。 It is preferable that at least one of Ar 1 , R 0 and R 1 in the above formula (1) has a hydroxy group or the above group (α). It is preferred that at least Ar 1 has a hydroxy group or a group (α).
Ａｒ１、Ｒ０及びＲ１は、ヒドロキシ基及び上記基（α）以外の置換基を有していてもよい。置換基としては、例えば炭素数１～１０の１価の鎖状炭化水素基、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、メトキシ基、エトキシ基、プロポキシ基等のアルコキシ基、フェノキシ基、ナフチルオキシ基等のアリールオキシ基、メトキシカルボニル基、エトキシカルボニル基等のアルコキシカルボニル基、メトキシカルボニルオキシ基、エトキシカルボニルオキシ基等のアルコキシカルボニルオキシ基、ホルミル基、アセチル基、プロピオニル基、ブチリル基等のアシル基、シアノ基、ニトロ基などが挙げられる。 Ar 1 , R 0 and R 1 may have a hydroxy group and a substituent other than the above group (α). Examples of the substituent include a monovalent chain hydrocarbon group having 1 to 10 carbon atoms, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, Aryloxy groups such as phenoxy group and naphthyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, alkoxycarbonyloxy groups such as methoxycarbonyloxy group and ethoxycarbonyloxy group, formyl group, acetyl group, propionyl group, Examples include acyl groups such as butyryl groups, cyano groups, and nitro groups.
上記式（１）で表される繰り返し単位としては、例えば下記式（１－１）～（１－２８）で表される繰り返し単位等が挙げられる。 Examples of the repeating unit represented by the above formula (1) include repeating units represented by the following formulas (1-1) to (1-28).
中でも、上記式（１－５）～（１－７）、（１－１１）～（１－１２）、（１－２１）～（１－２４）で表される繰り返し単位が好ましい。 Among these, repeating units represented by the above formulas (1-5) to (1-7), (1-11) to (1-12), and (1-21) to (1-24) are preferred.
（［Ａ１１］重合体の製造方法）
［Ａ１１］重合体は、代表的に、上記式（１）のＡｒ１を与えるフェノール性水酸基を有する前駆体としての芳香環化合物と、上記式（１）のＲ０を与える前駆体としてのアルデヒド誘導体との酸付加縮合により製造することができる。さらに、上記式（２－１）又は（２－２）で表される基（α）に対応するハロゲン化炭化水素へのフェノール性水酸基による求核置換反応により、置換基として基（α）を導入した［Ａ１１］重合体を製造することができる。酸触媒としては特に限定されず、公知の無機酸及び有機酸を用いることができる。反応後、分離、精製、乾燥等を経て［Ａ１１］重合体を得ることができる。反応溶媒としては、後述の［Ｂ］溶媒を好適に採用することができる。
([A11] Method for producing polymer)
[A11] The polymer typically includes an aromatic ring compound as a precursor having a phenolic hydroxyl group that provides Ar 1 of the above formula (1), and an aldehyde as a precursor that provides R 0 of the above formula (1). It can be produced by acid addition condensation with a derivative. Furthermore, a group (α) is added as a substituent by a nucleophilic substitution reaction with a phenolic hydroxyl group to a halogenated hydrocarbon corresponding to the group (α) represented by the above formula (2-1) or (2-2). The introduced [A11] polymer can be produced. The acid catalyst is not particularly limited, and known inorganic acids and organic acids can be used. After the reaction, the [A11] polymer can be obtained through separation, purification, drying, etc. As the reaction solvent, the below-mentioned [B] solvent can be suitably employed.
（その他の［Ａ１］重合体）
［Ａ１］重合体として、［Ａ１１］重合体以外に、レゾール系樹脂、ポリアリーレン系樹脂、トリアジン系樹脂、カリックスアレーン系樹脂等を用いることができる。これらの樹脂は公知の方法により製造することができる。
(Other [A1] polymers)
[A1] In addition to the [A11] polymer, resol resins, polyarylene resins, triazine resins, calixarene resins, and the like can be used as the [A1] polymer. These resins can be manufactured by known methods.
（レゾール系樹脂）
レゾール系樹脂は、フェノール性化合物と、アルデヒド類とをアルカリ性触媒を用いて反応させて得られる樹脂である。
(resol resin)
A resol resin is a resin obtained by reacting a phenolic compound and an aldehyde using an alkaline catalyst.
フェノール性化合物としては、例えば、
フェノール、クレゾール、キシレノール、レゾルシノール、ビスフェノールＡ等のフェノール類；
１－ナフトール、２－ナフトール、１，５－ジヒドロキシナフタレン、２，７－ジヒドロキシナフタレン、９，９－ビス（６－ヒドロキシナフチル）フルオレン等のナフトール類；
９－アントロール等のアントロール類；
１－ヒドロキシピレン、２－ヒドロキシピレン等のヒドロキシピレン類などが挙げられる。
Examples of phenolic compounds include:
Phenols such as phenol, cresol, xylenol, resorcinol, and bisphenol A;
Naphthols such as 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 9,9-bis(6-hydroxynaphthyl)fluorene;
9-Anthroles such as anthrole;
Examples include hydroxypyrenes such as 1-hydroxypyrene and 2-hydroxypyrene.
アルデヒド類としては、例えば
ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、１－ピレンカルボキシアルデヒド等のアルデヒド；
パラホルムアルデヒド、トリオキサン、パラアルデヒド等のアルデヒド源などが挙げられる。
Examples of aldehydes include aldehydes such as formaldehyde, acetaldehyde, benzaldehyde, and 1-pyrenecarboxaldehyde;
Examples include aldehyde sources such as paraformaldehyde, trioxane, and paraldehyde.
（ポリアリーレン系樹脂）
ポリアリーレン系樹脂は、アリーレン骨格を含む化合物に由来する構造単位を有する樹脂である。アリーレン骨格としては、例えばフェニレン骨格、ナフチレン骨格、ビフェニレン骨格等が挙げられる。
(Polyarylene resin)
A polyarylene resin is a resin having a structural unit derived from a compound containing an arylene skeleton. Examples of the arylene skeleton include a phenylene skeleton, a naphthylene skeleton, and a biphenylene skeleton.
ポリアリーレン系樹脂としては、例えばポリアリーレンエーテル、ポリアリーレンスルフィド、ポリアリーレンエーテルスルホン、ポリアリーレンエーテルケトン、ビフェニレン骨格を含む構造単位とアセナフチレン骨格を含む化合物に由来する構造単位とを有する樹脂等が挙げられる。 Examples of polyarylene resins include polyarylene ether, polyarylene sulfide, polyarylene ether sulfone, polyarylene ether ketone, and resins having structural units containing a biphenylene skeleton and structural units derived from compounds containing an acenaphthylene skeleton. It will be done.
（トリアジン系樹脂）
トリアジン系樹脂は、トリアジン骨格を有する化合物に由来する構造単位を有する樹脂である。トリアジン骨格を有する化合物としては、例えばメラミン化合物、シアヌル酸化合物等が挙げられる。
(Triazine resin)
A triazine-based resin is a resin having a structural unit derived from a compound having a triazine skeleton. Examples of compounds having a triazine skeleton include melamine compounds and cyanuric acid compounds.
（カリックスアレーン系樹脂）
カリックスアレーン系樹脂は、ヒドロキシ基が結合する芳香環が炭化水素基を介して複数個環状に結合した環状オリゴマー又はこのヒドロキシ基、芳香環及び炭化水素基が有する水素原子の一部若しくは全部が置換された化合物である。
(Calixarene resin)
Calixarene resins are cyclic oligomers in which a plurality of aromatic rings to which hydroxy groups are bonded are cyclically bonded via hydrocarbon groups, or in which some or all of the hydrogen atoms possessed by the hydroxy groups, aromatic rings, and hydrocarbon groups are substituted. It is a compound that has been
［Ａ１］重合体が、［Ａ１１］重合体、レゾール系樹脂、ポリアリーレン系樹脂又はトリアジン系樹脂である場合、主鎖の芳香環として多環縮合芳香環を有する［Ａ１］重合体の重量平均分子量の下限としては、５００が好ましく、１０００がより好ましく、１５００がさらに好ましい。上記分子量の上限としては、１００００が好ましく、７０００がより好ましく、５０００がさらに好ましい。主鎖の芳香環として単環芳香環を有する［Ａ１］重合体の重量平均分子量の下限としては、１０００が好ましく、３０００がより好ましく、５０００がさらに好ましい。上記分子量の上限としては、３００００が好ましく、２００００がより好ましく、１５０００がさらに好ましい。なお、重量平均分子量の測定方法は、実施例の記載による。 When the [A1] polymer is a [A11] polymer, resol resin, polyarylene resin, or triazine resin, the weight average of the [A1] polymer having a polycyclic condensed aromatic ring as the aromatic ring in the main chain. The lower limit of the molecular weight is preferably 500, more preferably 1000, and even more preferably 1500. The upper limit of the molecular weight is preferably 10,000, more preferably 7,000, and even more preferably 5,000. The lower limit of the weight average molecular weight of the [A1] polymer having a monocyclic aromatic ring as the main chain aromatic ring is preferably 1,000, more preferably 3,000, and even more preferably 5,000. The upper limit of the molecular weight is preferably 30,000, more preferably 20,000, and even more preferably 15,000. Note that the method for measuring the weight average molecular weight is as described in Examples.
［Ａ１］重合体がカリックスアレーン系樹脂である場合、［Ａ１］重合体の分子量の下限としては、５００が好ましく、７００がより好ましく、１，０００がさらに好ましい。上記分子量の上限としては、５，０００が好ましく、３，０００がより好ましく、１，５００がさらに好ましい。 When the [A1] polymer is a calixarene resin, the lower limit of the molecular weight of the [A1] polymer is preferably 500, more preferably 700, and even more preferably 1,000. The upper limit of the molecular weight is preferably 5,000, more preferably 3,000, and even more preferably 1,500.
（［Ａ２］芳香環含有化合物）
［Ａ２］芳香環含有化合物は、芳香環を有し、かつ分子量が６００以上３０００以下の化合物である限り特に限定されない（ただし、［Ａ１］重合体に該当する化合物を除く。）。
([A2] Aromatic ring-containing compound)
[A2] The aromatic ring-containing compound is not particularly limited as long as it has an aromatic ring and a molecular weight of 600 or more and 3000 or less (excluding compounds that correspond to [A1] polymers).
［Ａ２］芳香環含有化合物の炭素含有割合は、耐熱性の点で、８０質量％以上であることが好ましい。上記炭素含有割合の下限は、８２質量％がより好ましく、８５質量％がさらに好ましい。上記炭素含有割合の上限は、９８質量％が好ましく、９６質量％がさらに好ましい。 [A2] The carbon content of the aromatic ring-containing compound is preferably 80% by mass or more in terms of heat resistance. The lower limit of the carbon content ratio is more preferably 82% by mass, and even more preferably 85% by mass. The upper limit of the carbon content is preferably 98% by mass, more preferably 96% by mass.
［Ａ２］芳香環含有化合物は、下記式（３）で表される化合物（以下、「［Ａ２１］芳香環含有化合物」ともいう。）であることが好ましい。
Ｗは、置換又は非置換の環員数５～６０の芳香環を含むｑ価の基である。
Ｒａは、環員数５～４０の芳香環を含む１価の基である。
ｑは１～１０の整数である。ｑが２以上である場合、複数のＲａは、互いに同一又は異なる。）
[A2] The aromatic ring-containing compound is preferably a compound represented by the following formula (3) (hereinafter also referred to as "[A21] aromatic ring-containing compound").
W is a q-valent group containing a substituted or unsubstituted aromatic ring having 5 to 60 ring members.
R a is a monovalent group containing an aromatic ring having 5 to 40 ring members.
q is an integer from 1 to 10. When q is 2 or more, a plurality of R a's are the same or different from each other. )
上記Ｗにおける環員数５～６０の芳香環としては、［Ａ］化合物が有し得るとする上記環員数５～４０の芳香環を環員数６０まで拡張した芳香環を好適に採用することができる。Ｗで表される置換又は非置換の環員数５～６０の芳香環を含むｑ価の基としては、上記環員数５～６０の芳香環からｑ個の水素原子を除いた基が挙げられる。Ｗが置換基を有する場合の置換基としては、ヒドロキシ基、上記基（α）及びこれら以外の置換基として挙げた上記置換基を好適に採用することができる。 As the aromatic ring having 5 to 60 ring members in the above W, an aromatic ring obtained by expanding the aromatic ring having 5 to 40 ring members that the compound [A] may have to 60 ring members can be suitably employed. . The q-valent group containing a substituted or unsubstituted aromatic ring having 5 to 60 ring members represented by W includes a group obtained by removing q hydrogen atoms from the above-mentioned aromatic ring having 5 to 60 ring members. As the substituent when W has a substituent, the hydroxy group, the above group (α), and the above substituents listed as substituents other than these can be suitably employed.
上記Ｗの芳香環は、ベンゼン環、ナフタレン環、アントラセン環、フェナレン環、フェナントレン環、ピレン環、フルオレン環、ペリレン環及びコロネン環からなる群より選ばれる少なくとも１つの芳香族炭化水素環であることが好ましい。 The aromatic ring of W above is at least one aromatic hydrocarbon ring selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a phenalene ring, a phenanthrene ring, a pyrene ring, a fluorene ring, a perylene ring, and a coronene ring. is preferred.
上記Ｒａにおける環員数５～４０の芳香環としては、［Ａ］化合物が有し得るとする上記環員数５～４０の芳香環を好適に採用することができる。Ｒａで表される環員数５～４０の芳香環を含む１価の基としては、上記環員数５～４０の芳香環から１個の水素原子を除いた基が挙げられる。上記Ｒ４の芳香環は、ベンゼン環、ナフタレン環、アントラセン環、フェナレン環、フェナントレン環、ピレン環、フルオレン環、ペリレン環及びコロネン環からなる群より選ばれる少なくとも１つの芳香族炭化水素環であることが好ましい。Ｒａが置換基を有する場合の置換基としては、ヒドロキシ基、上記基（α）及びこれら以外の置換基として挙げた上記置換基を好適に採用することができる。 As the aromatic ring having 5 to 40 ring members in R a above, the aromatic ring having 5 to 40 ring members described above that the [A] compound may have can be suitably employed. The monovalent group containing an aromatic ring having 5 to 40 ring members represented by R a includes a group obtained by removing one hydrogen atom from the aromatic ring having 5 to 40 ring members. The aromatic ring R 4 is at least one aromatic hydrocarbon ring selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a phenalene ring, a phenanthrene ring, a pyrene ring, a fluorene ring, a perylene ring, and a coronene ring. It is preferable. As the substituent when R a has a substituent, a hydroxy group, the above group (α), and the above substituents listed as substituents other than these can be suitably employed.
上記Ｒａは、下記式（３－１）又は（３－２）で表される基であることが好ましい。
式（ｉｉ）中、Ｒ１３は、水素原子又は炭素数１～２０の１価の有機基である。Ｒ１４は、炭素数１～２０の１価の有機基である。
式（ｉｉｉ）中、Ｒ１５は、炭素数１～２０の１価の有機基である。
式（ｉｖ）中、Ｒ１６は、水素原子又は炭素数１～２０の１価の有機基である。）
The above R a is preferably a group represented by the following formula (3-1) or (3-2).
In formula (ii), R 13 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R 14 is a monovalent organic group having 1 to 20 carbon atoms.
In formula (iii), R 15 is a monovalent organic group having 1 to 20 carbon atoms.
In formula (iv), R 16 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. )
上記式（ｉ）、（ｉｉ）、（ｉｉｉ）及び（ｉｖ）において、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５及びＲ１６（以下、「Ｒ１１～Ｒ１６」と表記することもある。）で表される炭素数１～２０の１価の有機基としては、上記式（１）のＲ０及びＲ１で表される炭素数１～４０の１価の有機基のうち炭素数１～２０に対応する基が挙げられる。 In the above formulas (i), (ii), (iii) and (iv), R 11 , R 12 , R 13 , R 14 , R 15 and R 16 (hereinafter referred to as “R 11 to R 16 ”) Among the monovalent organic groups having 1 to 40 carbon atoms represented by R 0 and R 1 in the above formula (1), the monovalent organic group having 1 to 20 carbon atoms represented by Examples include groups corresponding to 1 to 20 carbon atoms.
上記式（３－１）及び（３－２）中、Ａｒ５、Ａｒ６及びＡｒ７（以下、「Ａｒ５～Ａｒ７」と表記することもある。）は、それぞれ独立して、上記式（３－１）及び（３－２）における隣接する２つの炭素原子とともに縮合環構造を形成する置換又は非置換の環員数６～２０の芳香環である。Ａｒ５～Ａｒ７における環員数６～２０の芳香環としては、［Ａ］化合物が有し得るとする上記環員数５～４０の芳香環のうち環員数６～２０に対応する芳香環を好適に採用することができる。 In the above formulas (3-1) and (3-2), Ar 5 , Ar 6 and Ar 7 (hereinafter sometimes referred to as "Ar 5 to Ar 7 ") are each independently represented by the above formula It is a substituted or unsubstituted aromatic ring having 6 to 20 ring members that forms a fused ring structure together with two adjacent carbon atoms in (3-1) and (3-2). The aromatic ring having 6 to 20 ring members in Ar 5 to Ar 7 is preferably an aromatic ring corresponding to 6 to 20 ring members among the above aromatic rings having 5 to 40 ring members that the [A] compound may have. can be adopted.
Ａｒ５～Ａｒ７が置換基を有する場合の置換基としては、ヒドロキシ基、上記基（α）及びこれら以外の置換基として挙げた上記置換基を好適に採用することができる。 When Ar 5 to Ar 7 have a substituent, the hydroxy group, the above group (α), and the above substituents listed as substituents other than these can be suitably employed.
上記式（３－１）及び（３－２）中、Ｌ１及びＬ２における芳香環を有する２価の有機基としては、［Ａ］化合物が有し得るとする上記環員数５～４０の芳香環から２個の水素原子を除いた置換又は非置換の基（以下、「基（β）」ともいう。）が好適に挙げられる。Ｌ１及びＬ２で表される芳香環を有する２価の有機基としては、当該基（β）と上記Ｒ１１～Ｒ１６で表される炭素数１～２０の１価の有機基から１個の水素原子を除いた基とを組み合わせた基であってもよい。Ｌ１及びＬ２で表される芳香環を有する２価の有機基としては、置換又は非置換の環員数６～１２のアレーンジイル基、置換又は非置換の炭素数２～１０のアルケンジイル基、炭素数２～１０のアルキンジイル基又はこれらの組み合わせが好ましく、ベンゼンジイル基、ナフタレンジイル基、エチレンジイル基、エチンジイル基又はこれらの組み合わせがより好ましく、ベンゼンジイル基又はベンゼンジイル基とエチンジイル基との組み合わせがさらに好ましい。 In the above formulas (3-1) and (3-2), the divalent organic group having an aromatic ring in L 1 and L 2 has the above-mentioned number of ring members of 5 to 40 that the [A] compound may have. Preferred examples include substituted or unsubstituted groups (hereinafter also referred to as "groups (β)") obtained by removing two hydrogen atoms from an aromatic ring. The divalent organic group having an aromatic ring represented by L 1 and L 2 is one of the group (β) and the monovalent organic group having 1 to 20 carbon atoms represented by R 11 to R 16 above. It may also be a group that is a combination of groups with hydrogen atoms removed. The divalent organic group having an aromatic ring represented by L 1 and L 2 includes a substituted or unsubstituted arenediyl group having 6 to 12 ring members, a substituted or unsubstituted alkenediyl group having 2 to 10 carbon atoms, a carbon Alkyndiyl groups of 2 to 10 or a combination thereof are preferred, benzenediyl groups, naphthalenediyl groups, ethylenediyl groups, ethinediyl groups or combinations thereof are more preferred, and benzenediyl groups or a combination of benzenediyl groups and ethinediyl groups are preferred. More preferred.
上記式（３－１）及び（３－２）中、Ｌ１及びＬ２は単結合であることが好ましい。 In the above formulas (3-1) and (3-2), L 1 and L 2 are preferably single bonds.
［Ａ２１］芳香環含有化合物としては、例えば下記式（３－１）～（３－１２）で表される化合物等が挙げられる。 [A21] Examples of the aromatic ring-containing compound include compounds represented by the following formulas (3-1) to (3-12).
［Ａ２１］芳香環含有化合物の合成方法としては、代表的には、出発原料として例えばフルオレンのケトンやアルキン置換体を準備し、触媒等の存在下でケトン部分やアルキン部分の環化反応を進行させることで合成することができる。その他の構造についても、出発原料やケトン体の構造等を適宜選択することで合成することができる。 [A21] A typical method for synthesizing an aromatic ring-containing compound is to prepare, for example, a ketone or alkyne substituted product of fluorene as a starting material, and proceed with a cyclization reaction of the ketone or alkyne moiety in the presence of a catalyst. It can be synthesized by Other structures can also be synthesized by appropriately selecting the starting materials, the structure of the ketone body, etc.
当該膜形成用組成物における［Ａ］化合物の含有割合の下限としては、［Ａ］化合物及び［Ｂ］溶媒の合計質量中、０．０１質量％が好ましく、０．０２質量％がより好ましく、０．１質量％がさらに好ましく、０．５質量％が特に好ましい。上記含有割合の上限としては、［Ａ］重合体及び［Ｂ］溶媒の合計質量中、５０質量％が好ましく、４０質量％がより好ましく、３０質量％がさらに好ましく、２０質量％が特に好ましい。 The lower limit of the content of the [A] compound in the film-forming composition is preferably 0.01% by mass, more preferably 0.02% by mass, based on the total mass of the [A] compound and the [B] solvent; 0.1% by mass is more preferred, and 0.5% by mass is particularly preferred. The upper limit of the content ratio is preferably 50% by mass, more preferably 40% by mass, even more preferably 30% by mass, and particularly preferably 20% by mass based on the total mass of the [A] polymer and [B] solvent.
＜［Ｂ］溶媒＞
［Ｂ］溶媒は、［Ａ］化合物及び必要に応じて含有する任意成分を溶解又は分散することができれば特に限定されない。
<[B] Solvent>
The [B] solvent is not particularly limited as long as it can dissolve or disperse the [A] compound and optional components contained therein.
［Ｂ］溶媒としては、例えば炭化水素系溶媒、エステル系溶媒、アルコール系溶媒、ケトン系溶媒、エーテル系溶媒、含窒素系溶媒などが挙げられる。［Ｂ］溶媒は、１種単独で又は２種以上を組み合わせて用いることができる。 [B] Examples of the solvent include hydrocarbon solvents, ester solvents, alcohol solvents, ketone solvents, ether solvents, and nitrogen-containing solvents. [B] Solvents can be used alone or in combination of two or more.
炭化水素系溶媒としては、例えばｎ－ペンタン、ｎ－ヘキサン、シクロヘキサン等の脂肪族炭化水素系溶媒、ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒などが挙げられる。 Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.
エステル系溶媒としては、例えばジエチルカーボネート等のカーボネート系溶媒、酢酸メチル、酢酸エチル等の酢酸モノエステル系溶媒、γ－ブチロラクトン等のラクトン系溶媒、酢酸ジエチレングリコールモノメチルエーテル、酢酸プロピレングリコールモノメチルエーテル等の多価アルコール部分エーテルカルボキシレート系溶媒、乳酸メチル、乳酸エチル等の乳酸エステル系溶媒などが挙げられる。 Examples of ester solvents include carbonate solvents such as diethyl carbonate, acetic acid monoester solvents such as methyl acetate and ethyl acetate, lactone solvents such as γ-butyrolactone, diethylene glycol monomethyl acetate, and propylene glycol monomethyl ether acetate. Examples include alcohol partial ether carboxylate solvents and lactic acid ester solvents such as methyl lactate and ethyl lactate.
アルコール系溶媒としては、例えばメタノール、エタノール、ｎ－プロパノール等のモノアルコール系溶媒、エチレングリコール、１，２－プロピレングリコール等の多価アルコール系溶媒などが挙げられる。 Examples of alcoholic solvents include monoalcoholic solvents such as methanol, ethanol, and n-propanol, and polyhydric alcoholic solvents such as ethylene glycol and 1,2-propylene glycol.
ケトン系溶媒としては、例えばメチルエチルケトン、メチルイソブチルケトン等の鎖状ケトン系溶媒、シクロヘキサノン等の環状ケトン系溶媒などが挙げられる。 Examples of the ketone solvent include chain ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and cyclic ketone solvents such as cyclohexanone.
エーテル系溶媒としては、例えばｎ－ブチルエーテル等の鎖状エーテル系溶媒、テトラヒドロフラン等の環状エーテル系溶媒等の多価アルコールエーテル系溶媒、ジエチレングリコールモノメチルエーテル等の多価アルコール部分エーテル系溶媒などが挙げられる。 Examples of ether solvents include chain ether solvents such as n-butyl ether, polyhydric alcohol ether solvents such as cyclic ether solvents such as tetrahydrofuran, and polyhydric alcohol partial ether solvents such as diethylene glycol monomethyl ether. .
含窒素系溶媒としては、例えばＮ，Ｎ－ジメチルアセトアミド等の鎖状含窒素系溶媒、Ｎ－メチルピロリドン等の環状含窒素系溶媒などが挙げられる。 Examples of nitrogen-containing solvents include chain nitrogen-containing solvents such as N,N-dimethylacetamide, and cyclic nitrogen-containing solvents such as N-methylpyrrolidone.
［Ｂ］溶媒としては、エステル系溶媒又はケトン系溶媒が好ましく、多価アルコール部分エーテルカルボキシレート系溶媒又は環状ケトン系溶媒がより好ましく、酢酸プロピレングリコールモノメチルエーテル又はシクロヘキサノンがさらに好ましい。 [B] The solvent is preferably an ester solvent or a ketone solvent, more preferably a polyhydric alcohol partial ether carboxylate solvent or a cyclic ketone solvent, and even more preferably propylene glycol monomethyl ether acetate or cyclohexanone.
当該組成物における［Ｂ］溶媒の含有割合の下限としては、５０質量％が好ましく、６０質量％がより好ましく、７０質量％がさらに好まく、８０質量％が特に好ましい。上記含有割合の上限としては、９９．９９質量％が好ましく、９９．９８質量％がより好ましく、９９．９質量％がさらに好ましく、９９．５質量％が特に好ましい。 The lower limit of the content of the [B] solvent in the composition is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and particularly preferably 80% by mass. The upper limit of the content ratio is preferably 99.99% by mass, more preferably 99.98% by mass, even more preferably 99.9% by mass, and particularly preferably 99.5% by mass.
［任意成分］
当該膜形成用組成物は、本発明の効果を損なわない範囲において任意成分を含有していてもよい。任意成分としては、例えば酸発生剤、架橋剤、界面活性剤、増感剤等が挙げられる。任意成分は、１種単独で又は２種以上を組み合わせて用いることができる。
[Optional ingredients]
The film-forming composition may contain optional components within a range that does not impair the effects of the present invention. Examples of optional components include acid generators, crosslinking agents, surfactants, and sensitizers. The optional components can be used alone or in combination of two or more.
［膜形成用組成物の調製方法］
当該組成物は、［Ａ］化合物、［Ｂ］溶媒、及び必要に応じて任意成分を所定の割合で混合し、好ましくは得られた混合物を孔径０．５μｍ以下のメンブランフィルター等でろ過することにより調製できる。
[Method for preparing film-forming composition]
The composition is prepared by mixing [A] the compound, [B] the solvent, and optional components in a predetermined ratio, and preferably filtering the resulting mixture using a membrane filter or the like with a pore size of 0.5 μm or less. It can be prepared by
《半導体基板の製造方法》
当該半導体基板の製造方法は、基板にイオン注入する工程（以下、「イオン注入工程」ともいう。）と、上記イオン注入工程後の上記基板の少なくともイオン注入領域に膜形成用組成物を塗工する工程（以下、「塗工工程」ともいう。）と、上記膜形成用組成物塗工工程により形成されたキャッピング膜を有する基板を１０００℃以上でアニーリングする工程（以下、「アニーリング工程」ともいう。）とを備える。
《Method for manufacturing semiconductor substrate》
The method for manufacturing the semiconductor substrate includes a step of implanting ions into the substrate (hereinafter also referred to as "ion implantation step"), and coating a film forming composition on at least the ion implantation region of the substrate after the ion implantation step. (hereinafter also referred to as the "coating process") and a process of annealing the substrate having the capping film formed by the film-forming composition coating process at 1000°C or higher (hereinafter also referred to as the "annealing process"). ).
当該半導体基板の製造方法は、上記アニーリング工程前に、上記膜形成用組成物塗工工程により形成されたキャッピング膜を１００℃以上６００℃以下で加熱する工程（以下、「膜加熱工程」ともいう。）を備えていてもよい。 The method for manufacturing the semiconductor substrate includes, before the annealing step, a step of heating the capping film formed by the film-forming composition coating step at 100° C. or more and 600° C. or less (hereinafter also referred to as "film heating step"). .) may be provided.
当該半導体基板の製造方法によれば、上記塗工工程において当該膜形成用組成物を用いることにより、高温アニーリングの際に高平坦性を基板表面に付与し得るキャッピング膜を形成するため、高品質の半導体基板を提供することができる。 According to the method for manufacturing a semiconductor substrate, the film-forming composition is used in the coating process to form a capping film that can impart high flatness to the substrate surface during high-temperature annealing. It is possible to provide a semiconductor substrate of.
以下、当該半導体基板の製造方法に用いる組成物及び各工程について説明する。 The composition and each step used in the method for manufacturing the semiconductor substrate will be described below.
［イオン注入工程］
イオン注入工程では、基板にイオン注入する。イオン注入領域以外の部分をマスク層で被覆した上でイオン注入を行うことが好ましい。マスク層としては有機膜や無機膜等の公知のマスク層を用いることができる。
[Ion implantation process]
In the ion implantation process, ions are implanted into the substrate. It is preferable to perform ion implantation after covering a portion other than the ion implantation region with a mask layer. As the mask layer, a known mask layer such as an organic film or an inorganic film can be used.
基板としては、炭化ケイ素、窒化ガリウム、ダイヤモンド、酸化ガリウム、窒化アルミニウム、ケイ素等のウェハが挙げられる。上記基板は、炭化ケイ素、窒化ガリウム及びダイヤモンドからなる群より選ばれる少なくとも１種を含むことが好ましい。基板表面には、銅、金、チタンなどの金属電極あるいは金属配線が形成されていてもよい。 Examples of the substrate include wafers of silicon carbide, gallium nitride, diamond, gallium oxide, aluminum nitride, silicon, and the like. Preferably, the substrate includes at least one selected from the group consisting of silicon carbide, gallium nitride, and diamond. Metal electrodes or metal wiring made of copper, gold, titanium, etc. may be formed on the surface of the substrate.
ドーパントとして注入されるイオンは公知の元素を用いることができ、ｐ型半導体領域の形成には、ホウ素、アルミニウム、ガリウム等が挙げられ、ｎ型半導体領域の形成には、窒素、リン、ヒ素等が挙げられる。 Known elements can be used as ions to be implanted as dopants, such as boron, aluminum, gallium, etc. for forming a p-type semiconductor region, and nitrogen, phosphorus, arsenic, etc. for forming an n-type semiconductor region. can be mentioned.
イオン注入温度の下限は、２００℃が好ましく、２５０℃がより好ましく、３００℃がさらに好ましい。イオン注入温度の上限は８００℃が好ましく、７００℃がより好ましく、６００℃がさらに好ましい。これにより、注入層の高温アニールによる再結晶化を促進して低抵抗層を形成することができ、また、ＳｉＣの熱酸化やステップバンチングを防止することができる。 The lower limit of the ion implantation temperature is preferably 200°C, more preferably 250°C, and even more preferably 300°C. The upper limit of the ion implantation temperature is preferably 800°C, more preferably 700°C, and even more preferably 600°C. Thereby, recrystallization of the injection layer by high-temperature annealing can be promoted to form a low-resistance layer, and thermal oxidation and step bunching of SiC can be prevented.
イオン注入エネルギーの下限は、１０ｋｅＶが好ましく、５０ｋｅＶがより好ましく、１００ｋｅＶがさらに好ましい。イオン注入エネルギーの上限は１５００ｋｅＶが好ましく、１０００ｋｅＶがより好ましく、５００ｋｅＶがさらに好ましい。 The lower limit of the ion implantation energy is preferably 10 keV, more preferably 50 keV, and even more preferably 100 keV. The upper limit of the ion implantation energy is preferably 1500 keV, more preferably 1000 keV, and even more preferably 500 keV.
イオン注入時の真空度の下限は、１．０×１０－５Ｐａが好ましく、１．０×１０－４Ｐａがより好ましく、２．０×１０－４Ｐａがさらに好ましい。上記真空度の上限は、１．０×１０－３Ｐａが好ましく、８．０×１０－４Ｐａがより好ましく、５．０×１０－４Ｐａがさらに好ましい。 The lower limit of the degree of vacuum during ion implantation is preferably 1.0×10 −5 Pa, more preferably 1.0×10 −4 Pa, and even more preferably 2.0×10 −4 Pa. The upper limit of the degree of vacuum is preferably 1.0×10 −3 Pa, more preferably 8.0×10 −4 Pa, and even more preferably 5.0×10 −4 Pa.
［マスク除去工程］
次に、必要に応じて、マスク層を除去する工程を行ってもよい。マスク層の除去は、アッシングやエッチング等により行うことができる。除去方法としてはアッシングが好ましい。アッシング温度は特に限定されないものの、２５℃以上２００℃以下の範囲にて好適に行うことができる。
[Mask removal process]
Next, if necessary, a step of removing the mask layer may be performed. The mask layer can be removed by ashing, etching, or the like. Ashing is preferred as the removal method. Although the ashing temperature is not particularly limited, it can be suitably carried out in a range of 25° C. or higher and 200° C. or lower.
［塗工工程］
本工程では、上記イオン注入工程後の上記基板の少なくともイオン注入領域に膜形成用組成物を塗工する。本工程では膜形成用組成物として、上述の当該膜形成用組成物を用いる。膜形成用組成物は、少なくともイオン注入領域に塗工すればよいものの、イオン注入領域外の領域を含めた所定領域にも塗工してもよく、基板表面全体に塗工してもよい。
[Coating process]
In this step, a film-forming composition is applied to at least the ion-implanted region of the substrate after the ion-implanting step. In this step, the above-mentioned film-forming composition is used as the film-forming composition. The film-forming composition may be applied to at least the ion-implanted region, but may also be applied to a predetermined region including an area outside the ion-implanted region, or may be applied to the entire surface of the substrate.
膜形成用組成物の塗工方法としては特に限定されず、例えば回転塗工、流延塗工、ロール塗工などの適宜の方法で実施することができる。これにより塗工膜が形成され、［Ｂ］溶媒の揮発などが起こることによりキャッピング膜が形成される。 The method for applying the film-forming composition is not particularly limited, and can be carried out by any suitable method such as spin coating, cast coating, or roll coating. A coating film is thereby formed, and a capping film is formed by volatilization of the [B] solvent.
［膜加熱工程］
次に、アニーリング工程前に、上記膜形成用組成物塗工工程により形成されたキャッピング膜を１００℃以上６００℃以下で加熱する膜加熱工程を行ってもよい。加熱によりキャッピング膜の形成が促進される。より詳細には、塗工膜の加熱により［Ｂ］溶媒の揮発等が促進される。また、［Ａ］化合物の硬化反応をより促進してキャッピング膜の耐熱性を向上させることができる。
[Membrane heating process]
Next, before the annealing step, a film heating step may be performed in which the capping film formed by the film forming composition coating step is heated at a temperature of 100° C. or more and 600° C. or less. Heating promotes the formation of the capping film. More specifically, heating the coating film promotes volatilization of the [B] solvent. In addition, the curing reaction of the [A] compound can be further promoted to improve the heat resistance of the capping film.
上記塗工膜の加熱は、大気雰囲気下で行ってもよいし、窒素雰囲気下で行ってもよい。加熱温度の下限としては、８０℃が好ましく、１２０℃がより好ましく、１６０℃がさらに好ましい。上記加熱温度の上限としては、６００℃が好ましく、５５０℃がより好ましく、５００℃がさらに好ましい。加熱における時間の下限としては、１５秒が好ましく、３０秒がより好ましい。上記時間の上限としては、５００秒が好ましく、３００秒がより好ましい。 The coating film may be heated in an air atmosphere or in a nitrogen atmosphere. The lower limit of the heating temperature is preferably 80°C, more preferably 120°C, and even more preferably 160°C. The upper limit of the heating temperature is preferably 600°C, more preferably 550°C, and even more preferably 500°C. The lower limit of the heating time is preferably 15 seconds, more preferably 30 seconds. The upper limit of the above time is preferably 500 seconds, more preferably 300 seconds.
形成されるキャッピング膜の平均厚みとの下限としては、１ｎｍが好ましく、３ｎｍがより好ましく、５ｎｍがさらに好ましく、１０ｎｍが特に好ましい。上記平均厚みの上限としては、２００μｍが好ましく、１５０μｍがより好ましく、１００μｍがさらに好ましく、８０μｍが特に好ましい。なお、平均厚みの測定方法は実施例の記載による。 The lower limit of the average thickness of the capping film to be formed is preferably 1 nm, more preferably 3 nm, even more preferably 5 nm, and particularly preferably 10 nm. The upper limit of the average thickness is preferably 200 μm, more preferably 150 μm, even more preferably 100 μm, and particularly preferably 80 μm. Note that the method for measuring the average thickness is as described in Examples.
［アニーリング工程］
上記膜形成用組成物塗工工程により形成されたキャッピング膜を有する基板を１０００℃以上でアニーリングする。これにより、イオン注入により損傷したＳｉＣ等の結晶を再結晶化させたり、イオンを効率的に拡散させて活性化させたりすることができる。アニーリング雰囲気は、大気雰囲気下でもよいものの、不活性ガス雰囲気下または水素添加不活性ガス雰囲気下であることが好ましい。アニーリング温度の下限は、１１００℃が好ましく、１３００℃がより好ましく、１５００℃がさらに好ましい。アニーリング温度の上限は、２３００℃が好ましく、２０００℃がより好ましく、１８００℃がさらに好ましい。
[Annealing process]
The substrate having the capping film formed by the above-described film-forming composition coating step is annealed at 1000° C. or higher. This makes it possible to recrystallize a crystal such as SiC that has been damaged by ion implantation, or to activate it by efficiently diffusing ions. Although the annealing atmosphere may be an air atmosphere, it is preferably an inert gas atmosphere or a hydrogenated inert gas atmosphere. The lower limit of the annealing temperature is preferably 1100°C, more preferably 1300°C, and even more preferably 1500°C. The upper limit of the annealing temperature is preferably 2300°C, more preferably 2000°C, and even more preferably 1800°C.
その後、酸素プラズマアッシング等によりキャッピング膜を除去し、基板表面に各種素子を公知の方法により形成していくことで、半導体基板を製造するとことができる。 Thereafter, the capping film is removed by oxygen plasma ashing or the like, and various elements are formed on the surface of the substrate by known methods, thereby manufacturing a semiconductor substrate.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically explained based on Examples, but the present invention is not limited to these Examples.
［重量平均分子量（Ｍｗ）］
重合体のＭｗは、東ソー（株）のＧＰＣカラム（「Ｇ２０００ＨＸＬ」２本、「Ｇ３０００ＨＸＬ」１本、及び「Ｇ４０００ＨＸＬ」１本）を用い、流量：１．０ｍＬ／分、溶出溶媒：テトラヒドロフラン、カラム温度：４０℃の分析条件で、単分散ポリスチレンを標準とするゲルパーミエーションクロマトグラフィー（検出器：示差屈折計）により測定した。
[Weight average molecular weight (Mw)]
The Mw of the polymer was determined using Tosoh Corporation GPC columns (2 G2000HXL, 1 G3000HXL, and 1 G4000HXL), flow rate: 1.0 mL/min, elution solvent: tetrahydrofuran, column. Measurement was performed by gel permeation chromatography (detector: differential refractometer) using monodisperse polystyrene as a standard under analysis conditions of temperature: 40°C.
［キャッピング膜の平均厚み］
キャッピング膜の平均厚みは、分光エリプソメータ（Ｊ．Ａ．ＷＯＯＬＬＡＭ社の「Ｍ２０００Ｄ」）を用いて、キャッピング膜の中心を含む５ｃｍ間隔の任意の９点の位置で膜厚を測定し、それらの膜厚の平均値を算出した値として求めた。
[Average thickness of capping film]
The average thickness of the capping film is determined by measuring the film thickness at nine arbitrary points at 5 cm intervals including the center of the capping film using a spectroscopic ellipsometer (J.A. WOOLLAM's "M2000D"). The average value of the thickness was determined as the calculated value.
［合成例１］（重合体（Ａ－１）の合成）
反応容器に、窒素雰囲気下、１－ヒドロキシピレン６１．２ｇ、ベンズアルデヒド３０．０ｇおよび１－ブタノール１８０．０ｇを仕込み、攪拌させて化合物を溶解させた。ｐ－トルエンスルホン酸１水和物５．３ｇの１－ブタノール溶液１０．０ｇを反応容器に添加した後、１００℃に加熱して８時間反応させた。反応終了後、反応溶液を分液ロートに移し、メチルイソブチルケトン２００ｇと水４００ｇを加えて有機相を洗浄した。水相を分離した後、得られた有機相を数回、水で洗浄した。その後、エバポレーターで濃縮し，残渣をメタノール５００ｇ中に滴下させて沈殿物を得た。沈殿物を吸引濾過により回収し、メタノール１００ｇで数回洗浄した。その後、真空乾燥機内にて６０℃で１２時間乾燥することにより、下記式（Ａ－１）で表される重合体（Ａ－１）を得た。重合体（Ａ－１）のＭｗは２，３００であった。
[Synthesis Example 1] (Synthesis of polymer (A-1))
A reaction vessel was charged with 61.2 g of 1-hydroxypyrene, 30.0 g of benzaldehyde, and 180.0 g of 1-butanol under a nitrogen atmosphere, and the mixture was stirred to dissolve the compounds. A solution of 5.3 g of p-toluenesulfonic acid monohydrate in 10.0 g of 1-butanol was added to the reaction vessel, and the mixture was heated to 100° C. and reacted for 8 hours. After the reaction was completed, the reaction solution was transferred to a separating funnel, and 200 g of methyl isobutyl ketone and 400 g of water were added to wash the organic phase. After separating the aqueous phase, the organic phase obtained was washed several times with water. Thereafter, it was concentrated using an evaporator, and the residue was dropped into 500 g of methanol to obtain a precipitate. The precipitate was collected by suction filtration and washed several times with 100 g of methanol. Thereafter, the polymer (A-1) represented by the following formula (A-1) was obtained by drying at 60° C. for 12 hours in a vacuum dryer. The Mw of the polymer (A-1) was 2,300.
［合成例２］（重合体（Ａ－２）の合成）
ベンズアルデヒド３０．０ｇの代わりに、ビフェニル－４－カルボキシアルデヒド５１．０ｇに変えたこと以外は［合成例１］と同様の条件で反応させることにより、下記式（Ａ－２）で表される重合体（Ａ－２）を得た。重合体（Ａ－２）のＭｗは２，８００であった。
[Synthesis Example 2] (Synthesis of polymer (A-2))
By reacting under the same conditions as [Synthesis Example 1] except that 51.0 g of biphenyl-4-carboxaldehyde was used instead of 30.0 g of benzaldehyde, a heavy compound represented by the following formula (A-2) was obtained. Combined product (A-2) was obtained. The M w of the polymer (A-2) was 2,800.
［合成例３］（重合体（Ａ－３）の合成）
ベンズアルデヒド３０．０ｇの代わりに、１－ナフトアルデヒド４４．０ｇに変えたこと以外は［合成例１］と同様の条件で反応させることにより、下記式（Ａ－３）で表される重合体（Ａ－３）を得た。重合体（Ａ－３）のＭｗは２，４００であった。
[Synthesis Example 3] (Synthesis of polymer (A-3))
By reacting under the same conditions as [Synthesis Example 1] except that 44.0 g of 1-naphthaldehyde was used instead of 30.0 g of benzaldehyde, a polymer represented by the following formula (A-3) ( A-3) was obtained. The Mw of the polymer (A-3) was 2,400.
［合成例４］（重合体（Ａ－４）の合成）
反応容器に、窒素雰囲気下、９，９－ビス（４－ヒドロキシフェニル）フルオレン３０．０ｇ、１－ナフトアルデヒド１３．３ｇおよび１－ブタノール８６．７ｇを仕込み、攪拌させて化合物を溶解させた。ｐ－トルエンスルホン酸１水和物１．６２ｇの１－ブタノール溶液５．０ｇを反応容器に添加した後、９０℃に加熱して１２時間反応させた。反応終了後、反応溶液を分液ロートに移し、メチルイソブチルケトン２００ｇと水４００ｇを加えて有機相を洗浄した。水相を分離した後、得られた有機相を数回、水で洗浄した。その後、エバポレーターで濃縮し，残渣をメタノール５００ｇ中に滴下させて沈殿物を得た。沈殿物を吸引濾過により回収し、メタノール１００ｇで数回洗浄した。その後、真空乾燥機内にて６０℃で１２時間乾燥することにより、下記式（Ａ－４）で表される重合体（Ａ－４）を得た。重合体（Ａ－４）のＭｗは４，０００であった。
[Synthesis Example 4] (Synthesis of polymer (A-4))
A reaction vessel was charged with 30.0 g of 9,9-bis(4-hydroxyphenyl)fluorene, 13.3 g of 1-naphthaldehyde, and 86.7 g of 1-butanol under a nitrogen atmosphere, and the mixture was stirred to dissolve the compounds. A solution of 1.62 g of p-toluenesulfonic acid monohydrate in 5.0 g of 1-butanol was added to the reaction vessel, and then heated to 90° C. and reacted for 12 hours. After the reaction was completed, the reaction solution was transferred to a separating funnel, and 200 g of methyl isobutyl ketone and 400 g of water were added to wash the organic phase. After separating the aqueous phase, the organic phase obtained was washed several times with water. Thereafter, it was concentrated using an evaporator, and the residue was dropped into 500 g of methanol to obtain a precipitate. The precipitate was collected by suction filtration and washed several times with 100 g of methanol. Thereafter, the polymer (A-4) represented by the following formula (A-4) was obtained by drying at 60° C. for 12 hours in a vacuum dryer. The Mw of the polymer (A-4) was 4,000.
［合成例５］（重合体（Ａ－５）の合成）
１－ナフトアルデヒド１３．３ｇの代わりに１－ピレンカルボキシアルデヒド１９．７ｇに変えたこと以外は［合成例４］と同様の条件で反応させることにより、下記式（Ａ－５）で表される重合体（Ａ－５）を得た。重合体（Ａ－５）のＭｗは３，５００であった。
[Synthesis Example 5] (Synthesis of polymer (A-5))
By reacting under the same conditions as [Synthesis Example 4] except that 19.7 g of 1-pyrenecarboxaldehyde was used instead of 13.3 g of 1-naphthaldehyde, a product represented by the following formula (A-5) was obtained. A polymer (A-5) was obtained. The Mw of the polymer (A-5) was 3,500.
［合成例６］（重合体（Ａ－６）の合成）
反応容器に、窒素雰囲気下、１－ヒドロキシピレン１０．８ｇ、１，１－ビス（４－ヒドロキシフェニル）－１－フェニルエタン９．５ｇ、１－ナフトール３７．１２ｇおよびパラホルムアルデヒド１０．０ｇを仕込み、続いてｐ－トルエンスルホン酸一水和物０．７ｇの１－ブタノール（２００ｇ）溶液を反応容器に添加した後、室温で攪拌させて化合物を溶解させた。その後、１００℃に加熱して１０時間反応させた。反応終了後、反応溶液を分液ロートに移し、メチルイソブチルケトン２００ｇと水４００ｇを加えて有機相を洗浄した。水相を分離した後、得られた有機相を数回、水で洗浄した。その後、エバポレーターで濃縮し，残渣をメタノール５００ｇ中に滴下させて沈殿物を得た。沈殿物を吸引濾過により回収し、メタノール１００ｇで数回洗浄した。その後、真空乾燥機内にて６０℃で１２時間乾燥することにより、重合体を得た（Ｍｗ＝２，８００）。さらに，得られた重合体５．０ｇをメチルイソブチルケトン２５．０ｇ、メタノール１２．０ｇ、テトラメチルアンモニウムヒドロキシド（２５％水溶液）１８．６ｇを加えて、室温で数分間攪拌させることで溶解させた。臭化プロパルギル６．０ｇを添加し、室温から６０℃に加熱して４時間反応させた。反応終了後、反応溶液を分液ロートに移し、メチルイソブチルケトン２００ｇと水２００ｇを加えて有機相を分離した。有機相を数回水で洗浄した後、得られた有機相をエバポレーターで濃縮し、メタノール２００ｇ中に滴下させて沈殿物を得た。沈殿物を吸引濾過により回収し、メタノール５０ｇで数回洗浄した。その後、真空乾燥機内にて６０℃で１２時間乾燥することにより、下記式（Ａ－６）で表される重合体（Ａ－６）を得た。重合体（Ａ－６）のＭｗは３，２００であった。下記式中、繰り返し単位の横に添えられている数字は各繰り返し単位の含有割合（モル％）を表す。以降の式中の数字も同様である。
[Synthesis Example 6] (Synthesis of polymer (A-6))
A reaction vessel was charged with 10.8 g of 1-hydroxypyrene, 9.5 g of 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 37.12 g of 1-naphthol, and 10.0 g of paraformaldehyde under a nitrogen atmosphere. Then, a solution of 0.7 g of p-toluenesulfonic acid monohydrate in 1-butanol (200 g) was added to the reaction vessel, and the mixture was stirred at room temperature to dissolve the compound. Thereafter, the mixture was heated to 100°C and reacted for 10 hours. After the reaction was completed, the reaction solution was transferred to a separating funnel, and 200 g of methyl isobutyl ketone and 400 g of water were added to wash the organic phase. After separating the aqueous phase, the organic phase obtained was washed several times with water. Thereafter, it was concentrated using an evaporator, and the residue was dropped into 500 g of methanol to obtain a precipitate. The precipitate was collected by suction filtration and washed several times with 100 g of methanol. Thereafter, a polymer was obtained by drying in a vacuum dryer at 60° C. for 12 hours (M w =2,800). Furthermore, 5.0 g of the obtained polymer was dissolved by adding 25.0 g of methyl isobutyl ketone, 12.0 g of methanol, and 18.6 g of tetramethylammonium hydroxide (25% aqueous solution) and stirring for several minutes at room temperature. Ta. 6.0 g of propargyl bromide was added, heated from room temperature to 60°C, and reacted for 4 hours. After the reaction was completed, the reaction solution was transferred to a separating funnel, and 200 g of methyl isobutyl ketone and 200 g of water were added to separate the organic phase. After washing the organic phase several times with water, the obtained organic phase was concentrated using an evaporator and dropped into 200 g of methanol to obtain a precipitate. The precipitate was collected by suction filtration and washed several times with 50 g of methanol. Thereafter, the polymer (A-6) represented by the following formula (A-6) was obtained by drying at 60° C. for 12 hours in a vacuum dryer. The Mw of the polymer (A-6) was 3,200. In the following formula, the number attached next to the repeating unit represents the content ratio (mol %) of each repeating unit. The same applies to the numbers in the following formulas.
［合成例７］（重合体（Ａ－７）の合成）
反応容器に、窒素雰囲気下、２，７－ジヒドロキシナフタレン１０７．２ｇ、パラホルムアルデヒド５０．７ｇおよび１－ブタノール３００．０ｇを仕込み、攪拌させて化合物を溶解させた。ｐ－トルエンスルホン酸１水和物３．２ｇの１－ブタノール溶液２０．０ｇを反応容器に添加した後、１００℃に加熱して８時間反応させた。反応終了後、反応溶液を分液ロートに移し、メチルイソブチルケトン２００ｇと水４００ｇを加えて有機相を洗浄した。水相を分離した後、得られた有機相を数回、水で洗浄した。その後、エバポレーターで濃縮し，残渣をメタノール５００ｇ中に滴下させて沈殿物を得た。沈殿物を吸引濾過により回収し、メタノール１００ｇで数回洗浄した。その後、真空乾燥機内にて６０℃で１２時間乾燥することにより、重合体（Ｍｗ＝２，０００）を得た。さらに，得られた重合体５．０ｇをメチルイソブチルケトン２５．０ｇ、メタノール１２．０ｇ、テトラメチルアンモニウムヒドロキシド（２５％水溶液）１８．６ｇを加えて、室温で数分間攪拌させることで溶解させた。臭化プロパルギル６．０ｇを添加し、室温から６０℃に加熱して４時間反応させた。反応終了後、反応溶液を分液ロートに移し、メチルイソブチルケトン２００ｇと水２００ｇを加えて有機相を分離した。有機相を数回水で洗浄した後、得られた有機相をエバポレーターで濃縮し、メタノール２００ｇ中に滴下させて沈殿物を得た。沈殿物を吸引濾過により回収し、メタノール５０ｇで数回洗浄した。その後、真空乾燥機内にて６０℃で１２時間乾燥することにより、下記式（Ａ－７）で表される重合体（Ａ－７）を得た。重合体（Ａ－７）のＭｗは２，２００であった。
[Synthesis Example 7] (Synthesis of polymer (A-7))
A reaction vessel was charged with 107.2 g of 2,7-dihydroxynaphthalene, 50.7 g of paraformaldehyde, and 300.0 g of 1-butanol under a nitrogen atmosphere, and the mixture was stirred to dissolve the compounds. A solution of 3.2 g of p-toluenesulfonic acid monohydrate in 20.0 g of 1-butanol was added to the reaction vessel, and then heated to 100° C. and reacted for 8 hours. After the reaction was completed, the reaction solution was transferred to a separating funnel, and 200 g of methyl isobutyl ketone and 400 g of water were added to wash the organic phase. After separating the aqueous phase, the organic phase obtained was washed several times with water. Thereafter, it was concentrated using an evaporator, and the residue was dropped into 500 g of methanol to obtain a precipitate. The precipitate was collected by suction filtration and washed several times with 100 g of methanol. Thereafter, a polymer (M w =2,000) was obtained by drying at 60° C. for 12 hours in a vacuum dryer. Furthermore, 5.0 g of the obtained polymer was dissolved by adding 25.0 g of methyl isobutyl ketone, 12.0 g of methanol, and 18.6 g of tetramethylammonium hydroxide (25% aqueous solution) and stirring for several minutes at room temperature. Ta. 6.0 g of propargyl bromide was added, heated from room temperature to 60°C, and reacted for 4 hours. After the reaction was completed, the reaction solution was transferred to a separating funnel, and 200 g of methyl isobutyl ketone and 200 g of water were added to separate the organic phase. After washing the organic phase several times with water, the obtained organic phase was concentrated using an evaporator and dropped into 200 g of methanol to obtain a precipitate. The precipitate was collected by suction filtration and washed several times with 50 g of methanol. Thereafter, the polymer (A-7) represented by the following formula (A-7) was obtained by drying in a vacuum dryer at 60° C. for 12 hours. The Mw of the polymer (A-7) was 2,200.
［合成例８］（化合物（Ａ－８）の合成）
反応容器に、窒素雰囲気下、１，３，５－ベンゼントリイルトリス－９Ｈ－フルオレン１０．０ｇ、シクロペンチルメチルエーテル８０．０ｇ、テトラメチルアンモニウムブロミド１．２ｇ、５０％水酸化ナトリウム水溶液１１．２ｇを加えて室温で数分間攪拌させた。臭化プロパルギル１６．５を添加して、８０℃で６時間反応させた。反応終了後、反応溶液を分液ロートに移し、メチルイソブチルケトンと１％シュウ酸水溶液を加えて有機相を分離した。得られた有機相を得られた有機相をエバポレーターで濃縮し、メタノール３００ｇ中に滴下させて沈殿物を得た。。沈殿物を吸引濾過により回収し、メタノール１００ｇで数回洗浄した。その後、真空乾燥機内にて６０℃で１２時間乾燥することにより、下記式（Ａ－８）で表される化合物（Ａ－８）を得た。
[Synthesis Example 8] (Synthesis of compound (A-8))
In a reaction vessel, under a nitrogen atmosphere, 10.0 g of 1,3,5-benzentriyltris-9H-fluorene, 80.0 g of cyclopentyl methyl ether, 1.2 g of tetramethylammonium bromide, and 11.2 g of 50% aqueous sodium hydroxide solution. was added and stirred for several minutes at room temperature. 16.5 grams of propargyl bromide was added and reacted at 80° C. for 6 hours. After the reaction was completed, the reaction solution was transferred to a separating funnel, and methyl isobutyl ketone and a 1% aqueous oxalic acid solution were added to separate the organic phase. The obtained organic phase was concentrated using an evaporator and dropped into 300 g of methanol to obtain a precipitate. . The precipitate was collected by suction filtration and washed several times with 100 g of methanol. Thereafter, the compound (A-8) represented by the following formula (A-8) was obtained by drying at 60° C. for 12 hours in a vacuum dryer.
［合成例９］（化合物（Ａ－９）の合成）
反応容器に、窒素雰囲気下、１，３，５－ベンゼントリイルトリス－９Ｈ－フルオレン１０．０ｇ、ｍ―エチニルベンズアルデヒド７．５ｇおよびテトラヒドロフラン９０．０ｇを加えて懸濁させた。２５％テトラメチルアンモニウムヒドロキシド４６．０ｇおよびテトラブチルアンモニウムブロミド１．１ｇを加え、６０℃で４時間反応させた。反応終了後、メチルイソブチルケトン２００．０ｇと５％シュウ酸水溶液２００．０ｇを加えて有機相を分離した。有機相を数回水で洗浄した後、得られた有機相をエバポレーターで濃縮し、メタノール２００ｇ中に滴下させて沈殿物を得た。沈殿物を吸引濾過により回収し、メタノール５０．０ｇで数回洗浄した。その後、真空乾燥機内にて６０℃で１２時間乾燥することにより、下記式（Ａ－９）で表される化合物（Ａ－９）を得た
[Synthesis Example 9] (Synthesis of compound (A-9))
10.0 g of 1,3,5-benzentriyltris-9H-fluorene, 7.5 g of m-ethynylbenzaldehyde and 90.0 g of tetrahydrofuran were added and suspended in a reaction vessel under a nitrogen atmosphere. 46.0 g of 25% tetramethylammonium hydroxide and 1.1 g of tetrabutylammonium bromide were added and reacted at 60°C for 4 hours. After the reaction was completed, 200.0 g of methyl isobutyl ketone and 200.0 g of a 5% aqueous oxalic acid solution were added to separate the organic phase. After washing the organic phase several times with water, the obtained organic phase was concentrated using an evaporator and dropped into 200 g of methanol to obtain a precipitate. The precipitate was collected by suction filtration and washed several times with 50.0 g of methanol. Thereafter, the compound (A-9) represented by the following formula (A-9) was obtained by drying at 60°C for 12 hours in a vacuum dryer.
［合成例１０］（化合物（Ａ－１０）の合成）
ｍ―エチニルベンズアルデヒド７．５ｇの代わりに、１－ナフトアルデヒド９．０ｇに変えたこと以外は［合成例９］と同様の条件で反応させることにより、下記式（Ａ－１０）で表される化合物（Ａ－１０）を得た。
[Synthesis Example 10] (Synthesis of compound (A-10))
By reacting under the same conditions as [Synthesis Example 9] except that 9.0 g of 1-naphthaldehyde was used instead of 7.5 g of m-ethynylbenzaldehyde, a product represented by the following formula (A-10) was obtained. Compound (A-10) was obtained.
［合成例１１］（化合物（Ａ－１１）の合成）
ｍ―エチニルベンズアルデヒド７．５ｇの代わりに、１－ピレンカルボキシアルデヒド１３．３ｇに変えたこと以外は［合成例９］と同様の条件で反応させることにより、下記式（Ａ－１１）で表される化合物（Ａ－１１）を得た。
[Synthesis Example 11] (Synthesis of compound (A-11))
By reacting under the same conditions as [Synthesis Example 9] except that 13.3 g of 1-pyrenecarboxaldehyde was used instead of 7.5 g of m-ethynylbenzaldehyde, a reaction product represented by the following formula (A-11) was obtained. Compound (A-11) was obtained.
［合成例１２］（重合体（Ａ－１２）の合成）
反応容器に、窒素雰囲気下、ｍ－クレゾール２５０．０ｇ、３７質量％ホルマリン１２５．０ｇおよび無水シュウ酸２．０ｇを加え、１００℃で３時間、１８０℃で１時間反応させた後、減圧下にて未反応モノマーを除去し、下記式（Ａ－１２）で表される重合体（Ａ－１２）を得た。得られた重合体（Ａ－１２）のＭｗは１１，０００であった。
[Synthesis Example 12] (Synthesis of polymer (A-12))
250.0 g of m-cresol, 125.0 g of 37% by mass formalin, and 2.0 g of oxalic anhydride were added to a reaction container under a nitrogen atmosphere, and the mixture was reacted at 100°C for 3 hours and at 180°C for 1 hour, and then reacted under reduced pressure. Unreacted monomers were removed to obtain a polymer (A-12) represented by the following formula (A-12). The Mw of the obtained polymer (A-12) was 11,000.
［比較例１］（重合体（Ｘ－１）の合成）
反応容器に、窒素雰囲気下、４－アセトキシスチレン８．６ｇ、スチレン１．４ｇおよびアゾビス（イソ酪酸）ジメチル３．１ｇ、メチルイソブチルケトン３０．０ｇを加えて室温で攪拌させた。その後、８０℃に昇温後６時間反応させた。重合後の反応溶液を室温まで冷却後、トリエチルアミン３０．０ｇおよびメタノール５４．０を添加して、さらに９０℃で６時間反応させることでアセトキシ基を脱保護させた。１％シュウ酸水溶液１００．０ｇを加えて有機相を分離した。有機相を数回水で洗浄した後、得られた有機相をエバポレーターで濃縮し、ヘキサン２００ｇ中に滴下させて沈殿物を得た。沈殿物を吸引濾過により回収し、ヘキサン５０．０ｇで数回洗浄した。その後、真空乾燥機内にて溶媒留去することにより、下記式（Ｘ－１）で表される重合体（Ｘ－１）を得た。
[Comparative Example 1] (Synthesis of polymer (X-1))
8.6 g of 4-acetoxystyrene, 1.4 g of styrene, 3.1 g of dimethyl azobis(isobutyrate), and 30.0 g of methyl isobutyl ketone were added to a reaction vessel under a nitrogen atmosphere, and the mixture was stirred at room temperature. Thereafter, the temperature was raised to 80°C and the reaction was carried out for 6 hours. After cooling the reaction solution after polymerization to room temperature, 30.0 g of triethylamine and 54.0 g of methanol were added, and the reaction was further carried out at 90° C. for 6 hours to deprotect the acetoxy group. 100.0 g of a 1% aqueous oxalic acid solution was added and the organic phase was separated. After washing the organic phase several times with water, the obtained organic phase was concentrated using an evaporator and dropped into 200 g of hexane to obtain a precipitate. The precipitate was collected by suction filtration and washed several times with 50.0 g of hexane. Thereafter, the solvent was distilled off in a vacuum dryer to obtain a polymer (X-1) represented by the following formula (X-1).
＜組成物の調製＞
組成物の調製に用いた［Ａ］化合物、［Ｂ］溶媒、［Ｃ］酸発生剤及び［Ｄ］架橋剤について以下に示す。
<Preparation of composition>
The [A] compound, [B] solvent, [C] acid generator, and [D] crosslinking agent used in the preparation of the composition are shown below.
［［Ａ］化合物］
実施例：上記合成した重合体（Ａ－１）～（Ａ－７）、（Ａ－１２）、化合物（Ａ－８）～（Ａ－１１）
比較例：上記合成した重合体（Ｘ－１）
[[A] Compound]
Examples: Polymers (A-1) to (A-7), (A-12), compounds (A-8) to (A-11) synthesized above
Comparative example: Polymer synthesized above (X-1)
［［Ｂ］溶媒］
Ｂ－１：酢酸プロピレングリコールモノメチルエーテル
Ｂ－２：シクロヘキサノン
[[B] Solvent]
B-1: Propylene glycol monomethyl ether acetate B-2: Cyclohexanone
［［Ｃ］酸発生剤］
Ｃ－１：下記式（Ｃ－１）で表される化合物）
[[C] Acid generator]
C-1: compound represented by the following formula (C-1))
［［Ｄ］架橋剤］
Ｄ－１：下記式（Ｄ－１）で表される化合物
[[D] Crosslinking agent]
D-1: Compound represented by the following formula (D-1)
Ｄ－２：下記式（Ｄ－２）で表される化合物 D-2: Compound represented by the following formula (D-2)
［実施例１］
［Ａ］化合物としての（Ａ－１）１４質量部を［Ｂ］溶媒としての（Ｂ－１）８６質量部に溶解した。得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン（ＰＴＦＥ）メンブランフィルターでろ過して、組成物（Ｊ－１）を調製した。
[Example 1]
[A] 14 parts by mass of (A-1) as a compound was dissolved in 86 parts by mass of (B-1) as a [B] solvent. The resulting solution was filtered through a polytetrafluoroethylene (PTFE) membrane filter with a pore size of 0.45 μm to prepare a composition (J-1).
［実施例２～２７及び比較例１］
下記表１に示す種類及び含有量の各成分を使用したこと以外は、実施例１と同様にして組成物（Ｊ－２）～（Ｊ－２７）及び（ＣＪ－１）を調製した。表１中の「［Ｃ］酸発生剤」及び「［Ｄ］架橋剤」の列における「－」は、該当する成分を使用しなかったことを示す。
[Examples 2 to 27 and Comparative Example 1]
Compositions (J-2) to (J-27) and (CJ-1) were prepared in the same manner as in Example 1, except that the types and contents of each component shown in Table 1 below were used. In Table 1, "-" in the "[C] acid generator" and "[D] crosslinking agent" columns indicates that the corresponding component was not used.
＜評価＞
上記得られた組成物を用い、平坦性について下記方法により評価を行った。評価結果を下記表２に合わせて示す。
<Evaluation>
Using the composition obtained above, flatness was evaluated by the following method. The evaluation results are also shown in Table 2 below.
［平坦性］
上記調製した組成物を、ＳｉＣ（基板）上に、スピンコーターで回転塗工法により塗工した。次に、大気雰囲気下にて２００℃で６０秒間加熱した後、２３℃で６０秒間冷却することにより、平均厚み５０ｎｍの膜を形成し、基板上にキャッピング膜が形成された膜付き基板を得た。基板を窒素雰囲気下にて１７００℃まで加熱して３分間保持したのち、キャッピング膜を酸素プラズマアッシングにより除去し、ＳｉＣ（基板）の表面の粗さを原子間力顕微鏡（日立ハイテクサイエンス社製）によって測定した。ＳｉＣ（基板）の中央部の１００ｎｍ幅の直線上を１０ｎｍの等間隔で１０点測定し、それらの平均の深さと最大の深さの差をＳｉＣ（基板）の表面の粗さとした。ＳｉＣ（基板）の表面の粗さが０．５ｎｍ未満の場合は「Ａ」（良好）とし、０．５ｎｍ以上の場合は「Ｂ」（不良）と評価した。
[Flatness]
The composition prepared above was applied onto SiC (substrate) by a spin coating method using a spin coater. Next, a film with an average thickness of 50 nm was formed by heating at 200°C for 60 seconds in an air atmosphere and then cooling at 23°C for 60 seconds to obtain a film-coated substrate with a capping film formed on the substrate. Ta. After heating the substrate to 1700°C in a nitrogen atmosphere and holding it for 3 minutes, the capping film was removed by oxygen plasma ashing, and the surface roughness of the SiC (substrate) was measured using an atomic force microscope (manufactured by Hitachi High-Tech Science). Measured by. Ten points were measured at equal intervals of 10 nm on a straight line with a width of 100 nm at the center of the SiC (substrate), and the difference between the average depth and the maximum depth was taken as the roughness of the surface of the SiC (substrate). When the surface roughness of SiC (substrate) was less than 0.5 nm, it was evaluated as "A" (good), and when it was 0.5 nm or more, it was evaluated as "B" (poor).
表２の結果から分かるように、実施例の組成物から形成されたキャッピング膜は、比較例の組成物から形成されたキャッピングと比較して、平坦性に優れていた。 As can be seen from the results in Table 2, the capping film formed from the composition of the Example had excellent flatness compared to the capping film formed from the composition of the Comparative Example.
本発明の膜形成用組成物によれば、高温アニーリングの際に高平坦性を基板表面に付与し得るキャッピング膜を効率的に形成することができる。本発明の半導体基板の製造方法によれば、高温アニーリングの際に高平坦性を基板表面に付与し得るキャッピング膜を形成するため、高品質の半導体基板を提供することができる。従って、これらは、今後さらに高機能化が進行すると予想される半導体デバイスの製造等に好適に用いることができる。 According to the film-forming composition of the present invention, a capping film that can impart high flatness to a substrate surface during high-temperature annealing can be efficiently formed. According to the method for manufacturing a semiconductor substrate of the present invention, a capping film that can impart high flatness to the substrate surface during high-temperature annealing is formed, so that a high-quality semiconductor substrate can be provided. Therefore, these can be suitably used in the production of semiconductor devices, which are expected to become more sophisticated in the future.
Claims (15)
芳香環を有する化合物と、
溶媒と
を含み、
上記芳香環を有する化合物が、主鎖に芳香環を有する重合体、分子量が６００以上３０００以下の芳香環含有化合物又はこれらの組み合わせである、膜形成用組成物。 A film-forming composition for forming a capping film in an annealing step after an ion implantation step into a substrate in the production of a semiconductor substrate, the composition comprising:
A compound having an aromatic ring,
containing a solvent and
A composition for forming a film, wherein the compound having an aromatic ring is a polymer having an aromatic ring in the main chain, an aromatic ring-containing compound having a molecular weight of 600 or more and 3000 or less, or a combination thereof.
上記イオン注入工程後の上記基板の少なくともイオン注入領域に膜形成用組成物を塗工する工程と、
上記膜形成用組成物塗工工程により形成されたキャッピング膜を有する基板を１０００℃以上でアニーリングする工程と
を備え、
上記膜形成用組成物が、
芳香環を有する化合物と、
溶媒と
を含み、
上記芳香環を有する化合物が、主鎖に芳香環を有する樹脂、分子量が６００以上３０００以下の芳香環含有化合物又はこれらの組み合わせである、半導体基板の製造方法。 A step of implanting ions into the substrate,
a step of applying a film-forming composition to at least the ion-implanted region of the substrate after the ion-implanting step;
a step of annealing the substrate having the capping film formed by the film-forming composition coating step at 1000° C. or higher;
The film-forming composition described above is
A compound having an aromatic ring,
containing a solvent and
A method for producing a semiconductor substrate, wherein the compound having an aromatic ring is a resin having an aromatic ring in its main chain, an aromatic ring-containing compound having a molecular weight of 600 or more and 3000 or less, or a combination thereof.
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2022
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