JP2011114163A - Coating liquid for element isolation material and method for preparing the same, thin film for element isolation layer and method for forming the same, and substrate and method for manufacturing the same - Google Patents
Coating liquid for element isolation material and method for preparing the same, thin film for element isolation layer and method for forming the same, and substrate and method for manufacturing the same Download PDFInfo
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- JP2011114163A JP2011114163A JP2009269325A JP2009269325A JP2011114163A JP 2011114163 A JP2011114163 A JP 2011114163A JP 2009269325 A JP2009269325 A JP 2009269325A JP 2009269325 A JP2009269325 A JP 2009269325A JP 2011114163 A JP2011114163 A JP 2011114163A
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- Prior art keywords
- element isolation
- insulating film
- forming
- group
- coating
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- 238000000576 coating method Methods 0.000 title claims abstract description 112
- 239000011248 coating agent Substances 0.000 title claims abstract description 104
- 238000002955 isolation Methods 0.000 title claims abstract description 81
- 239000007788 liquid Substances 0.000 title claims abstract description 74
- 239000000758 substrate Substances 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 59
- 239000010409 thin film Substances 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000002243 precursor Substances 0.000 claims abstract description 55
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 38
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- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 23
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 129
- 239000000243 solution Substances 0.000 claims description 32
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- 238000002360 preparation method Methods 0.000 claims description 23
- 125000000962 organic group Chemical group 0.000 claims description 14
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
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- 239000003093 cationic surfactant Substances 0.000 description 1
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- 238000002484 cyclic voltammetry Methods 0.000 description 1
- LMKPHJYTFHAGHK-UHFFFAOYSA-N cyclodrine Chemical compound C1CCCC1(O)C(C(=O)OCCN(CC)CC)C1=CC=CC=C1 LMKPHJYTFHAGHK-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
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- 238000003618 dip coating Methods 0.000 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 239000002241 glass-ceramic Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
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- 238000002329 infrared spectrum Methods 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 239000000231 karaya gum Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- VPOQIALCYVGVOS-UHFFFAOYSA-N methyl(propoxy)silane Chemical compound CCCO[SiH2]C VPOQIALCYVGVOS-UHFFFAOYSA-N 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KRKPYFLIYNGWTE-UHFFFAOYSA-N n,o-dimethylhydroxylamine Chemical compound CNOC KRKPYFLIYNGWTE-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
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- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 230000002123 temporal effect Effects 0.000 description 1
- OQTSOKXAWXRIAC-UHFFFAOYSA-N tetrabutan-2-yl silicate Chemical compound CCC(C)O[Si](OC(C)CC)(OC(C)CC)OC(C)CC OQTSOKXAWXRIAC-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- BCLLLHFGVQKVKL-UHFFFAOYSA-N tetratert-butyl silicate Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BCLLLHFGVQKVKL-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical group C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Formation Of Insulating Films (AREA)
- Element Separation (AREA)
Abstract
【課題】基板と素子分離層との剥離やクラックが発生し難く、凹状の溝を有する基板上に平坦な素子分離層を形成することができる素子分離材料用塗布液等を提供する。
【解決手段】半導体装置のシャロートレンチアイソレーション構造の素子分離層の形成に用いられる素子分離材料用塗布液は、アルコキシシラン化合物が加水分解、縮合された絶縁膜形成前駆体と、絶縁膜形成前駆体の濃度を所望の濃度に調製する溶媒と、を備えている。絶縁膜形成前駆体は、（Ｓｉ−Ｏ）の繰り返し単位を主骨格としたポリマーであり、その分子の末端に炭素数２〜６個のアルコキシル基を有している。
【選択図】なしDisclosed is a coating liquid for an element isolation material that can form a flat element isolation layer on a substrate having a concave groove, which is unlikely to cause peeling or cracking between the substrate and the element isolation layer.
An element isolation material coating solution used for forming an element isolation layer having a shallow trench isolation structure of a semiconductor device includes an insulating film forming precursor obtained by hydrolysis and condensation of an alkoxysilane compound, and an insulating film forming precursor. And a solvent for adjusting the body concentration to a desired concentration. The insulating film forming precursor is a polymer having a repeating unit of (Si—O) as a main skeleton, and has an alkoxyl group having 2 to 6 carbon atoms at the end of the molecule.
[Selection figure] None
Description
本発明は、半導体装置のシャロートレンチアイソレーション（ＳＴＩ：Shallow Trench Isolation）構造に用いられる素子分離材料用塗布液、素子分離材料用塗布液の作製方法、素子分離層用薄膜、素子分離層用薄膜の形成方法、基板、及び、基板の形成方法に関する。 The present invention relates to a coating liquid for element isolation material used in a shallow trench isolation (STI) structure of a semiconductor device, a method for producing a coating liquid for element isolation material, a thin film for element isolation layer, and a thin film for element isolation layer The present invention relates to a method for forming a substrate, a substrate, and a method for forming a substrate.
半導体素子製造時に基板に凹状の溝（トレンチ溝）を形成し、その溝内に素子分離層、例えば、シリコン酸化膜を成膜することで、ＳＴＩ構造を作製する技術が広く利用されている。このようにトレンチ溝内に成膜されるシリコン酸化膜は、電気的に各素子を分離する役割を持つことから、絶縁性、耐電圧性など優れた電気的特性が必要となる。 A technique for forming an STI structure is widely used by forming a concave groove (trench groove) in a substrate at the time of manufacturing a semiconductor element and forming an element isolation layer, for example, a silicon oxide film in the groove. As described above, the silicon oxide film formed in the trench groove has a role of electrically isolating each element, and therefore requires excellent electrical characteristics such as insulation and voltage resistance.
一般にＳＴＩ構造のトレンチ溝に、シリコン酸化膜を形成する手法としては、ＣＶＤ（Chemical Vapor Deposition）やスパッタなどの乾式で膜を形成する方法や、有機溶剤に溶解、若しくは分散したポリシラザンやシリコーン樹脂をスピンコート等の手法により塗布する方法（特許文献１〜４参照）が提案、実施されている。 In general, as a method of forming a silicon oxide film in a trench groove having an STI structure, a dry film forming method such as CVD (Chemical Vapor Deposition) or sputtering, or polysilazane or silicone resin dissolved or dispersed in an organic solvent is used. A method of applying by a technique such as spin coating (see Patent Documents 1 to 4) has been proposed and implemented.
ＣＶＤやスパッタなどの乾式膜形成方法は、膜材料を基板上部から堆積させるものであり、凹状の溝構造がそのまま維持され易く、また、高アスペクト比の凹（トレンチ）構造を埋め込むことは困難である。このため、局所的にボイドが発生したり、高品位なシリコン酸化膜が得られにくくなる。また、これらの手法では膜の形成に時間を要することや、装置が非常に高価になるという問題もある。 The dry film forming method such as CVD or sputtering deposits the film material from the upper part of the substrate, and the concave groove structure is easily maintained as it is, and it is difficult to embed a high aspect ratio concave (trench) structure. is there. For this reason, voids are generated locally, and it is difficult to obtain a high-quality silicon oxide film. In addition, these methods have problems that it takes time to form a film and that the apparatus becomes very expensive.
一方、ポリシラザンやシリコーン樹脂を塗布する方法では、短時間で薄膜の形成が可能であるが、塗布後の乾燥、熱処理工程で溶剤の揮発や膜成分の硬化に伴う薄膜の収縮が起こり、これによって凹部の底部や側面で基板と薄膜との剥離やクラックが生じ易いという問題がある。特に、ポリシラザン系の材料においては、窒素原子等の不純物が膜内に残留して、シリコン酸化膜の電気的特性を悪化させるなど、高品質なシリコン酸化膜を得ることが困難である。 On the other hand, in the method of applying polysilazane and silicone resin, a thin film can be formed in a short time, but the film shrinks due to the volatilization of the solvent and the hardening of the film components in the drying and heat treatment processes after the application. There is a problem that peeling or cracking between the substrate and the thin film tends to occur at the bottom or side of the recess. In particular, in a polysilazane-based material, it is difficult to obtain a high-quality silicon oxide film, for example, impurities such as nitrogen atoms remain in the film to deteriorate the electrical characteristics of the silicon oxide film.
また、これらのいずれの方法も、溝を含む基板全体にシリコン酸化膜を形成した後に、ＣＭＰ(化学的機械研磨：Chemical Mechanical Polishing)処理を施すことにより溝内部のみにシリコン酸化膜を残す工程を必要としている。このＣＭＰ処理により半導体素子へのダメージが発生し、歩留まりの低下を招く原因となってしまう。このため、ＣＭＰ処理を施すことなく（ＣＭＰレス工程で）、溝内部にシリコン酸化膜を形成することが求められている。 In any of these methods, after a silicon oxide film is formed on the entire substrate including the trench, a CMP (Chemical Mechanical Polishing) process is performed to leave the silicon oxide film only in the trench. In need of. This CMP process causes damage to the semiconductor element, which causes a decrease in yield. For this reason, it is required to form a silicon oxide film inside the trench without performing a CMP process (in a CMP-less process).
本発明は、上記実情に鑑みてなされたものであり、基板と素子分離層との剥離やクラックが発生し難く、凹状の溝を有する基板上に平坦な素子分離層を形成することができる素子分離材料用塗布液、素子分離材料用塗布液の作製方法、素子分離層用薄膜、素子分離層用薄膜の形成方法、基板、及び、基板の形成方法を提供することを目的とする。
また、本発明は、ＣＭＰレス工程で溝内部にシリコン酸化膜を形成するための素子分離材料用塗布液、素子分離材料用塗布液の作製方法、素子分離層用薄膜、素子分離層用薄膜の形成方法、基板、及び、基板の形成方法を提供することを目的とする。
The present invention has been made in view of the above circumstances, and it is difficult for peeling and cracking between the substrate and the element isolation layer, and an element capable of forming a flat element isolation layer on a substrate having a concave groove. It is an object of the present invention to provide a separation material coating liquid, a method for producing an element separation material coating liquid, a device separation layer thin film, a device separation layer thin film formation method, a substrate, and a substrate formation method.
The present invention also provides an element isolation material coating solution for forming a silicon oxide film inside a groove in a CMP-less process, a method for producing an element isolation material coating solution, an element isolation layer thin film, and an element isolation layer thin film. It is an object to provide a forming method, a substrate, and a forming method of the substrate.
上記目的を達成するため、本発明の第１の観点に係る素子分離材料用塗布液は、
半導体装置のシャロートレンチアイソレーション構造の素子分離層の形成に用いられる素子分離材料用塗布液であって、
アルコキシシラン化合物が加水分解、縮合された絶縁膜形成前駆体と、
前記絶縁膜形成前駆体の濃度を所望の濃度に調製する溶媒と、を備え、
前記絶縁膜形成前駆体は、（Ｓｉ−Ｏ）の繰り返し単位を主骨格としたポリマーであり、その分子の末端に炭素数２〜６個のアルコキシル基を有している、ことを特徴とする。
In order to achieve the above object, an element separating material coating liquid according to the first aspect of the present invention comprises:
An element isolation material coating liquid used for forming an element isolation layer of a shallow trench isolation structure of a semiconductor device,
An insulating film forming precursor in which an alkoxysilane compound is hydrolyzed and condensed;
A solvent for adjusting the concentration of the insulating film forming precursor to a desired concentration, and
The insulating film forming precursor is a polymer having a repeating unit of (Si—O) as a main skeleton, and has an alkoxyl group having 2 to 6 carbon atoms at the end of the molecule. .
前記アルコキシシラン化合物は、例えば、
Ｓｉ（ＯＲ１）４（Ｒ１は炭素数２〜６個の有機基を示す。）で表される第１のアルコキシシラン化合物と、
Ｒ２ ｎＳｉ（ＯＲ３）４−ｎ（Ｒ２はメチル基、エチル基、プロピル基、ビニル基、または、フェニル基を示す。Ｒ３は炭素数２〜６個の有機基を示す。ｎは１〜３の整数である。）で表される第２のアルコキシシラン化合物と、が、混合されている。
The alkoxysilane compound is, for example,
A first alkoxysilane compound represented by Si (OR 1 ) 4 (R 1 represents an organic group having 2 to 6 carbon atoms);
R 2 n Si (OR 3 ) 4-n (R 2 represents a methyl group, an ethyl group, a propyl group, a vinyl group, or a phenyl group. R 3 represents an organic group having 2 to 6 carbon atoms. N Is an integer of 1 to 3.) and a second alkoxysilane compound represented by
本発明の第２の観点に係る素子分離材料用塗布液の作製方法は、
半導体装置のシャロートレンチアイソレーション構造の素子分離層の形成に用いられる素子分離材料用塗布液の作製方法であって、
アルコキシシラン化合物と第１の溶媒との混合液を作製する混合液作製工程と、
前記混合液作製工程により作製された混合液を加水分解、縮合して絶縁膜形成前駆体を作製する絶縁膜形成前駆体作製工程と、
前記絶縁膜形成前駆体作製工程により作製された絶縁膜形成前駆体に第２の溶媒を加えることにより塗布液を作製する塗布液作製工程と、を備え、
前記混合液作製工程では、前記アルコキシシラン化合物に、炭素数２〜６個のアルコキシル基を有するアルコキシシラン化合物を用いる、ことを特徴とする。
The method for producing the coating liquid for element isolation material according to the second aspect of the present invention is as follows:
A method for producing a coating liquid for an element isolation material used for forming an element isolation layer having a shallow trench isolation structure of a semiconductor device,
A mixed liquid preparation step of preparing a mixed liquid of the alkoxysilane compound and the first solvent;
An insulating film forming precursor manufacturing step of preparing an insulating film forming precursor by hydrolyzing and condensing the mixed liquid prepared by the mixed liquid manufacturing step;
A coating liquid preparation step of preparing a coating liquid by adding a second solvent to the insulating film formation precursor prepared by the insulating film formation precursor preparation step,
In the mixed liquid preparation step, an alkoxysilane compound having an alkoxyl group having 2 to 6 carbon atoms is used as the alkoxysilane compound.
前記混合液作製工程では、前記アルコキシシラン化合物に、例えば、
Ｓｉ（ＯＲ１）４（Ｒ１は炭素数２〜６個の有機基を示す。）で表される第１のアルコキシシラン化合物と、
Ｒ２ ｎＳｉ（ＯＲ３）４−ｎ（Ｒ２はメチル基、エチル基、プロピル基、ビニル基、または、フェニル基を示す。Ｒ３は炭素数２〜６個の有機基を示す。ｎは１〜３の整数である。）で表される第２のアルコキシシラン化合物と、の混合物を用いる。
In the mixed liquid preparation step, for example, the alkoxysilane compound includes:
A first alkoxysilane compound represented by Si (OR 1 ) 4 (R 1 represents an organic group having 2 to 6 carbon atoms);
R 2 n Si (OR 3 ) 4-n (R 2 represents a methyl group, an ethyl group, a propyl group, a vinyl group, or a phenyl group. R 3 represents an organic group having 2 to 6 carbon atoms. N Is an integer of 1 to 3.) and a mixture with a second alkoxysilane compound represented by:
前記絶縁膜形成前駆体作製工程では、前記混合液に加水分解触媒及び水を加えた溶液を３０℃以下の温度で加水分解させる加水分解工程と、
前記加水分解工程で加水分解された溶液を４０℃以上の温度で縮合反応を進める縮合反応工程と、
前記縮合反応工程で縮合反応が進められた溶液を、減圧下で前記加水分解工程で加えられた水および一部の加水分解触媒と溶媒を除去する除去工程と、
を備えていることが好ましい。
In the insulating film formation precursor preparation step, a hydrolysis step of hydrolyzing a solution obtained by adding a hydrolysis catalyst and water to the mixed solution at a temperature of 30 ° C. or less;
A condensation reaction step of advancing the condensation reaction of the solution hydrolyzed in the hydrolysis step at a temperature of 40 ° C. or higher;
A removal step of removing the water and a part of the hydrolysis catalyst and the solvent added in the hydrolysis step under reduced pressure from the solution subjected to the condensation reaction in the condensation reaction step;
It is preferable to provide.
本発明の第３の観点に係る素子分離層用薄膜の形成方法は、
本発明の第１の観点に係る素子分離材料用塗布液を塗布して塗膜を形成する塗膜形成工程と、
前記塗膜形成工程により形成された塗膜中の溶媒を除去して塗膜を乾燥させる乾燥工程と、
前記乾燥工程により乾燥された塗膜を焼成して素子分離層用薄膜を形成する薄膜形成工程と、
を備える、ことを特徴とする。
The method for forming a thin film for an element isolation layer according to the third aspect of the present invention includes:
A coating film forming step of forming a coating film by applying the coating liquid for element isolation material according to the first aspect of the present invention;
A drying step of drying the coating film by removing the solvent in the coating film formed by the coating film forming step;
A thin film forming step of baking the coating film dried by the drying step to form a thin film for an element isolation layer;
It is characterized by comprising.
本発明の第４の観点に係る素子分離層用薄膜は、
本発明の第３の観点に係る素子分離層用薄膜の形成方法により形成された、ことを特徴とする。
The element isolation layer thin film according to the fourth aspect of the present invention provides:
It is formed by the method for forming a thin film for an element isolation layer according to the third aspect of the present invention.
本発明の第５の観点に係る基板は、
シャロートレンチアイソレーション構造を有する基板であって、
トレンチ構造を有するシリコン基板上に、本発明の第３の観点に係る素子分離層用薄膜の形成方法により形成した薄膜を有することを特徴とする。
The substrate according to the fifth aspect of the present invention is:
A substrate having a shallow trench isolation structure,
A thin film formed by the method for forming a thin film for an element isolation layer according to the third aspect of the present invention is provided on a silicon substrate having a trench structure.
本発明の第６の観点に係る基板の形成方法は、
シャロートレンチアイソレーション構造を有する基板の形成方法であって、
トレンチ構造を有するシリコン基板上に、本発明の第３の観点に係る素子分離層用薄膜の形成方法により薄膜を形成する、ことを特徴とする。
A method for forming a substrate according to a sixth aspect of the present invention includes:
A method of forming a substrate having a shallow trench isolation structure,
A thin film is formed on a silicon substrate having a trench structure by the method for forming a thin film for an element isolation layer according to the third aspect of the present invention.
本発明によれば、基板と素子分離層との剥離やクラックが発生し難く、凹状の溝を有する基板上に平坦な素子分離層を形成することができる。 According to the present invention, peeling and cracking between the substrate and the element isolation layer hardly occur, and a flat element isolation layer can be formed on a substrate having a concave groove.
以下、本発明の素子分離材料用塗布液、素子分離材料用塗布液の作製方法、素子分離層用薄膜、素子分離層用薄膜の形成方法、基板、及び、基板の形成方法について説明する。 Hereinafter, an element isolation material coating liquid, a method for producing an element isolation material coating liquid, an element isolation layer thin film, an element isolation layer thin film formation method, a substrate, and a substrate formation method will be described.
（素子分離材料用塗布液）
まず、本発明の素子分離材料用塗布液について説明する。本発明の塗布液は、半導体装置のシャロートレンチアイソレーション（ＳＴＩ）構造の素子分離層の形成に用いられる素子分離材料用塗布液であって、アルコキシシラン化合物が加水分解、縮合された絶縁膜形成前駆体と、絶縁膜形成前駆体の濃度を所望の濃度に調製する溶媒とを備えている。絶縁膜形成前駆体は、（Ｓｉ−Ｏ）の繰り返し単位を主骨格としたポリマーであり、その分子の末端に炭素数２〜６個のアルコキシル基を有している。
(Element isolation material coating solution)
First, the coating liquid for element isolation material of the present invention will be described. The coating liquid of the present invention is an element isolation material coating liquid used for forming an element isolation layer having a shallow trench isolation (STI) structure of a semiconductor device, and is an insulating film formed by hydrolysis and condensation of an alkoxysilane compound. A precursor and a solvent for adjusting the concentration of the insulating film forming precursor to a desired concentration are provided. The insulating film forming precursor is a polymer having a repeating unit of (Si—O) as a main skeleton, and has an alkoxyl group having 2 to 6 carbon atoms at the end of the molecule.
絶縁膜形成前駆体の分子の末端に炭素数１個のアルコキシル基を有する場合、アルコキシル基が加水分解しやすく、安定性が十分ではない。このような塗布液では、経時的に変化する可能性が高く、また、塗布工程においても雰囲気中の水分の影響を受けやすく安定的に使用することが困難となるためである。
一方、絶縁膜形成前駆体が炭素数７以上のアルコキシル基を有する場合、絶縁膜形成前駆体調製時の加水分解反応が進行し難く、絶縁膜形成前駆体の分子量調整が困難となる。また、アルコキシル基（置換基）が大きくなるために、加熱処理時の脱離による体積収縮が大きくなり、所望の効果が得られ難くなる。
また、絶縁膜形成前駆体の分子の末端がアルコキシル基でない、例えば、Ｓｉ-ＯＨの場合には、塗布液中の経時的な変化が顕著で、安定的に使用することが難しくなってしまう。
In the case where an alkoxyl group having 1 carbon atom is present at the end of the molecule of the insulating film forming precursor, the alkoxyl group is easily hydrolyzed and the stability is not sufficient. This is because such a coating solution is likely to change over time, and is also easily affected by moisture in the atmosphere in the coating process, making it difficult to use it stably.
On the other hand, when the insulating film forming precursor has an alkoxyl group having 7 or more carbon atoms, the hydrolysis reaction during the preparation of the insulating film forming precursor is difficult to proceed, and it is difficult to adjust the molecular weight of the insulating film forming precursor. In addition, since the alkoxyl group (substituent) becomes large, volume shrinkage due to desorption during the heat treatment becomes large, making it difficult to obtain a desired effect.
In addition, in the case where the terminal of the molecule of the insulating film forming precursor is not an alkoxyl group, for example, Si—OH, the change with time in the coating solution is remarkable, and it becomes difficult to use it stably.
炭素数２〜６個のアルコキシル基としては、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、イソブトキシ基、sec−ブトキシ基、tert−ブトキシ基、ペントキシ基、ヘキソキシ基、シクロペントキシ基、シクロヘキソキシ基、アセチルアセトナート基などが挙げられる。絶縁膜形成前駆体は、反応の制御のしやすさ、コスト等の観点から、その分子の末端に炭素数２〜４個のアルコキシル基を有していることが好ましい。このような絶縁膜形成前駆体は、後述するように、例えば、炭素数２〜６個のアルコキシ基を持つアルコキシシラン化合物を加水分解、重縮合することにより形成されている。 Examples of the alkoxyl group having 2 to 6 carbon atoms include ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy, cyclopent Examples thereof include a toxi group, a cyclohexoxy group, and an acetylacetonate group. The insulating film forming precursor preferably has an alkoxyl group having 2 to 4 carbon atoms at the end of the molecule from the viewpoint of easy control of reaction, cost, and the like. Such an insulating film forming precursor is formed, for example, by hydrolyzing and polycondensing an alkoxysilane compound having an alkoxy group having 2 to 6 carbon atoms, as will be described later.
溶媒としては、モノアルコール系、多価アルコール系、多価アルコール部分エーテル系、ケトン系、エステル系のいずれかの溶媒、若しくは、これらの混合溶媒などが挙げられる。 Examples of the solvent include monoalcohol-based, polyhydric alcohol-based, polyhydric alcohol partial ether-based, ketone-based, ester-based solvents, and mixed solvents thereof.
モノアルコール系の溶媒としては、例えば、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、ペンタノール、ヘキサノール、オクタノール、シクロヘキサノール、ベンジルアルコールなどが挙げられる。
多価アルコール系の溶媒としては、例えば、エチレングリコール、プロピレングリコール、ブチレングリコール、ジエチレングリコール、ジプロピレングリコールなどが挙げられる。
多価アルコール部分エーテル系の溶媒としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテルなどが挙げられる。
Examples of the monoalcohol solvent include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, octanol, cyclohexanol, and benzyl alcohol.
Examples of the polyhydric alcohol solvent include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, and dipropylene glycol.
Examples of the polyhydric alcohol partial ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol. Examples include monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether. It is.
ケトン系の溶媒としては、例えば、アセトン、メチルエチルケトン、メチル−ｎ−プロピルケトン、メチル−ｎ−ブチルケトン、ジエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどが挙げられる。
エステル系の溶媒としては、例えば、ジエチルカーボネート、炭酸エチレン、炭酸プロピレン、炭酸ジエチル、酢酸メチル、酢酸エチル、γ−ブチロラクトン、γ−バレロラクトン、酢酸ｎ−プロピル、酢酸イソプロピル、酢酸ｎ−ブチル、酢酸イソブチル、酢酸エチレングリコールモノメチルエーテル、酢酸エチレングリコールモノエチルエーテル、酢酸ジエチレングリコールモノメチルエーテル、酢酸ジエチレングリコールモノエチルエーテル、酢酸ジエチレングリコールモノ−ｎ−ブチルエーテル、酢酸プロピレングリコールモノメチルエーテル、酢酸プロピレングリコールモノエチルエーテル、酢酸プロピレングリコールモノプロピルエーテル、酢酸プロピレングリコールモノブチルエーテル、酢酸ジプロピレングリコールモノメチルエーテル、酢酸ジプロピレングリコールモノエチルエーテル、プロピオン酸メチル、プロピオン酸エチルなどが挙げられる。
これらの溶媒は、単独で用いても、２種以上を組み合わせて用いてもよい。
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, and acetic acid. Isobutyl, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol acetate Monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl acetate Examples include ether, dipropylene glycol monoethyl ether, methyl propionate, and ethyl propionate.
These solvents may be used alone or in combination of two or more.
本発明の塗布液の固形分濃度としては、塗布液が塗布可能な粘度になるような濃度であればよく、例えば、０．５〜５０ｗｔ％程度であり、コーティング方式や、膜厚の設定によっても最適値は異なるが、塗布液の経時的変化の観点から、１〜３５ｗｔ％であることが好ましい。 The solid content concentration of the coating solution of the present invention may be any concentration that allows the coating solution to be applied, and is, for example, about 0.5 to 50 wt%, depending on the coating method and the film thickness setting. Although the optimum value is different, it is preferably 1 to 35 wt% from the viewpoint of the change over time of the coating solution.
このように、本発明の塗布液では、絶縁膜形成前駆体が炭素数２〜６個のアルコキシル基を有するので、後述する塗布膜の乾燥、焼成工程で、絶縁膜形成前駆体分子の運動が容易になる。これにより、形成される薄膜（素子分離層）表面の平坦度が向上する。また、置換基の分解、収縮が起こる際に、骨格が固定化するタイミングが遅くなり、結果として、収縮に伴う応力が緩和され、クラック等が発生し難くなる。なお、分子の末端がＳｉ-ＯＨのような活性な構造の場合には、乾燥段階で、既に骨格の成長が進み、固定化されるため、薄膜の収縮時の応力が緩和されず、クラックの発生が起こり易くなる。 As described above, in the coating liquid of the present invention, the insulating film forming precursor has an alkoxyl group having 2 to 6 carbon atoms, and therefore the motion of the insulating film forming precursor molecules is caused in the coating film drying and baking processes described later. It becomes easy. Thereby, the flatness of the surface of the formed thin film (element isolation layer) is improved. In addition, when the substituent is decomposed or contracted, the timing at which the skeleton is immobilized is delayed. As a result, the stress accompanying the contraction is relieved and cracks and the like are hardly generated. In the case where the end of the molecule has an active structure such as Si—OH, the growth of the skeleton has already progressed and fixed in the drying stage, so that the stress at the time of contraction of the thin film is not relaxed, and cracks are not generated. Occurrence is likely to occur.
また、絶縁膜形成前駆体がアルコキシル基を有するので、後述する塗布膜の焼成過程で、アルコキシル基が分解された際に、その末端が活性状態になる。このため、塗布膜（薄膜）と基板との相互作用若しくは結合を形成し、薄膜と基板との密着性が向上する。なお、分子の末端がＳｉ-ＯＨの場合には、焼成過程において、活性基が減少するのみで、薄膜と基板との相互作用や結合の形成が行われにくく、このため、薄膜と基板との密着性が得られにくくなる。 Further, since the insulating film forming precursor has an alkoxyl group, when the alkoxyl group is decomposed in the baking process of the coating film described later, the terminal becomes active. For this reason, the interaction or bond between the coating film (thin film) and the substrate is formed, and the adhesion between the thin film and the substrate is improved. In the case where the end of the molecule is Si—OH, only the active groups are reduced in the baking process, and the interaction between the thin film and the substrate and the formation of bonds are difficult to occur. Adhesion is difficult to obtain.
さらに、絶縁膜形成前駆体が炭素数２〜６個のアルコキシル基を有するので、絶縁膜形成前駆体自体の経時安定性が良く、塗布工程においても雰囲気の影響を受け難く、安定的に使用しやすくなる。 Furthermore, since the insulating film forming precursor has an alkoxyl group having 2 to 6 carbon atoms, the temporal stability of the insulating film forming precursor itself is good, and it is not easily affected by the atmosphere in the coating process and is used stably. It becomes easy.
なお、本発明の塗布液に、必要に応じて界面活性剤を添加してもよい。この界面活性剤としては、例えば、ノニオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤などが挙げられ、さらには、シリコーン系界面活性剤、ポリアルキレンオキシド系界面活性剤、含フッ素界面活性剤などを挙げることができる。また、本発明の塗布液に、本発明の効果を阻害しない範囲内で公知の添加剤、例えば、成膜助剤、滑剤などを添加していてもよい。また、フィラーとして、コロイド状シリカやコロイド状アルミナなどの金属酸化物粒子を添加してもよい。 In addition, you may add surfactant to the coating liquid of this invention as needed. Examples of this surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Furthermore, silicone-based surfactants, polyalkylene oxide-based surfactants are exemplified. An activator, a fluorine-containing surfactant, etc. can be mentioned. In addition, a known additive such as a film forming aid or a lubricant may be added to the coating solution of the present invention as long as the effects of the present invention are not impaired. Moreover, you may add metal oxide particles, such as colloidal silica and colloidal alumina, as a filler.
（素子分離材料用塗布液の作製方法）
次に、素子分離材料用塗布液の作製方法について説明する。本発明の塗布液の作製方法は、半導体装置のＳＴＩ構造の素子分離層の形成に用いられる素子分離材料用塗布液の作成方法であって、アルコキシシラン化合物と溶媒との混合液を作製する混合液作製工程と、作製した混合液を加水分解、縮合して絶縁膜形成前駆体を作製する絶縁膜形成前駆体作製工程と、作製した絶縁膜形成前駆体に溶媒を加えることにより塗布液を作製する塗布液作製工程と、を備えている。
(Method for producing coating liquid for element isolation material)
Next, a method for producing a coating liquid for element isolation material will be described. The method for producing a coating liquid of the present invention is a method for producing a coating liquid for an element isolation material used for forming an element isolation layer having an STI structure of a semiconductor device, and a mixture for producing a mixed liquid of an alkoxysilane compound and a solvent. A liquid preparation process, an insulating film formation precursor preparation process for preparing an insulating film forming precursor by hydrolyzing and condensing the prepared mixed liquid, and a coating liquid is prepared by adding a solvent to the prepared insulating film forming precursor And a coating liquid preparation step.
混合液作製工程では、アルコキシシラン化合物に溶媒を加え、混合液を作製する。 In the mixed liquid preparation step, a solvent is added to the alkoxysilane compound to prepare a mixed liquid.
混合液作製工程で用いられるアルコキシシラン化合物としては、例えば、炭素数２〜６個のアルコキシル基を有するアルコキシシラン化合物が挙げられる。このように、炭素数２〜６個のアルコキシル基を有するので、絶縁膜形成前駆体自体の経時安定性が良く、塗布工程において、雰囲気の影響を受け難く、安定的に使用することができる。 Examples of the alkoxysilane compound used in the mixed liquid preparation step include an alkoxysilane compound having an alkoxyl group having 2 to 6 carbon atoms. As described above, since the alkoxyl group having 2 to 6 carbon atoms is contained, the insulating film forming precursor itself has good stability over time, and is hardly affected by the atmosphere in the coating process and can be used stably.
このようなアルコキシシラン化合物は、前述のように、反応の制御のしやすさ、コスト等の観点から、その分子の末端に炭素数２〜４個のアルコキシル基を有していることが好ましい。 As described above, such an alkoxysilane compound preferably has an alkoxyl group having 2 to 4 carbon atoms at the end of the molecule from the viewpoint of easy control of the reaction, cost, and the like.
このようなアルコキシシラン化合物としては、例えば、テトラエトキシシラン、テトラ−ｎ−プロポキシシラン、テトライソプロポキシシラン、テトラ−ｎ−ブトキシシラン、テトライソブトキシシラン、テトラ−ｓｅｃ−ブトキシシラン、テトラ−ｔｅｒｔ−ブトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリイソプロポキシシラン、エチルトリエトキシシラン、プロピルトリエトキシシラン、フェニルトリエトキシシラン、ビニルトリエトキシシラン、ジメチルジエトキシシラン、ジフェニルジエトキシシラン、トリメチルエトキシシランなどが挙げられる。アルコキシシラン化合物は、単独で用いても、２種以上を組み合わせて用いてもよい。 Examples of such alkoxysilane compounds include tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert- Butoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltriethoxysilane, propyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, trimethyl And ethoxysilane. An alkoxysilane compound may be used independently or may be used in combination of 2 or more type.
ここで、アルコキシシラン化合物は、以下に示すアルコキシシラン化合物Ａと、アルコキシシラン化合物Ｂとを混合して使用することが好ましい。
アルコキシシラン化合物Ａ：Ｓｉ（ＯＲ１）４
（なお、Ｒ１は炭素数２〜６個の有機基を示す。すなわち、ＯＲ１は炭素数２〜６個のアルコキシル基を示す。）
アルコキシシラン化合物Ｂ：Ｒ２ ｎＳｉ（ＯＲ３）４−ｎ
（Ｒ２はメチル基、エチル基、プロピル基、ビニル基、または、フェニル基を示す。Ｒ３は炭素数２〜６個の有機基を示す。すなわち、ＯＲ３は炭素数２〜６個のアルコキシル基を示す。ｎは１〜３の整数である。）
Here, the alkoxysilane compound is preferably used by mixing the alkoxysilane compound A shown below and the alkoxysilane compound B.
Alkoxysilane compound A: Si (OR 1 ) 4
(R 1 represents an organic group having 2 to 6 carbon atoms. That is, OR 1 represents an alkoxyl group having 2 to 6 carbon atoms.)
Alkoxysilane compound B: R 2 n Si (OR 3 ) 4-n
(R 2 represents a methyl group, an ethyl group, a propyl group, a vinyl group, or a phenyl group. R 3 represents an organic group having 2 to 6 carbon atoms. That is, OR 3 represents an organic group having 2 to 6 carbon atoms. Represents an alkoxyl group, n is an integer of 1 to 3)
有機基としては、例えば、アルキル基、アリール基、アリル基、グリシジル基などが挙げられ、炭素数２〜６個の有機基としては、例えば、エチル基、プロピル基、ブチル基、フェニル基などが挙げられる。これらの有機基は、その有する水素原子の一部又は全部がフッ素原子等に置換されていてもよい。 Examples of the organic group include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Examples of the organic group having 2 to 6 carbon atoms include an ethyl group, a propyl group, a butyl group, and a phenyl group. Can be mentioned. In these organic groups, some or all of the hydrogen atoms contained therein may be substituted with fluorine atoms or the like.
アルコキシシラン化合物の原料としてアルコキシシラン化合物Ａの他にアルコキシシラン化合物Ｂを混合して使用することにより、後述する塗布液の焼成工程時に発生する薄膜の収縮に伴う応力発生を効果的に抑制することができる。これは、アルコキシシラン化合物ＢのＲ２置換基は、焼成工程中に熱若しくは酸化分解され骨格を形成するが、絶縁膜形成前駆体が有するアルコキシル基と分解温度が異なるため、前述のアルコキシル基の効果を助長することとなる。また、Ｒ２としてメチル基、又は、フェニル基とすることが好ましい。これらがＳｉに結合した置換基は比較的耐熱性が高く、例えば、３００℃以上の加熱処理により分解が進行するためである。 By using the alkoxysilane compound B in addition to the alkoxysilane compound A as a raw material for the alkoxysilane compound, it is possible to effectively suppress the generation of stress accompanying shrinkage of the thin film that occurs during the coating liquid baking process described later. Can do. This is because the R 2 substituent of the alkoxysilane compound B is thermally or oxidatively decomposed during the firing step to form a skeleton, but since the decomposition temperature is different from the alkoxyl group of the insulating film forming precursor, The effect will be promoted. R 2 is preferably a methyl group or a phenyl group. This is because substituents in which these are bonded to Si have relatively high heat resistance, and, for example, decomposition proceeds by heat treatment at 300 ° C. or higher.
アルコキシシラン化合物の例としては、先にも挙げたが、その中で、好ましいものとしては以下が挙げられる。
アルコキシシラン化合物Ａとしては、例えば、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシランなどが挙げられる。アルコキシシラン化合物Ｂとしては、例えば、メチルトリエトキシシラン、メチルトリプロポキシシラン、フェニルトリエトキシシラン、ジメチルジエトキシシラン、トリメチルエトキシシランなどが挙げられる。
Examples of the alkoxysilane compound have been mentioned above. Among them, the following are preferable.
Examples of the alkoxysilane compound A include tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Examples of the alkoxysilane compound B include methyltriethoxysilane, methyltripropoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane, and trimethylethoxysilane.
アルコキシシラン化合物との混合液を形成する溶媒としては、モノアルコール系、多価アルコール系、多価アルコール部分エーテル系、ケトン系、エステル系などの適当な極性溶媒が用いられる。 As a solvent for forming a mixed liquid with an alkoxysilane compound, a suitable polar solvent such as a monoalcohol-based, polyhydric alcohol-based, polyhydric alcohol partial ether-based, ketone-based or ester-based solvent is used.
モノアルコール系、多価アルコール系、多価アルコール部分エーテル系、ケトン系、エステル系の溶媒は、前述の塗布液の溶媒のところで挙げたものと同様のものが挙げられる。 Examples of the monoalcohol-based, polyhydric alcohol-based, polyhydric alcohol partial ether-based, ketone-based, and ester-based solvents are the same as those described above for the solvent of the coating solution.
このような溶媒をアルコキシシラン化合物に所定量を加えることにより、混合液が作製される。この溶媒の量は、アルコキシシラン化合物の種類、形成される塗布液の塗布方法等によって異なるが、アルコキシシラン化合物中の全アルコキシル基１モルに対して、例えば、０．１〜１０モルの範囲で選定される。 A liquid mixture is prepared by adding a predetermined amount of such a solvent to the alkoxysilane compound. The amount of the solvent varies depending on the type of the alkoxysilane compound, the coating method of the coating solution to be formed, etc., but is, for example, in the range of 0.1 to 10 mol with respect to 1 mol of all alkoxyl groups in the alkoxysilane compound. Selected.
絶縁膜形成前駆体作製工程では、混合液作製工程で作製された混合液に、加水分解触媒と水とを加え、加水分解、縮合させ、絶縁膜形成前駆体を作製する。 In the insulating film formation precursor preparation step, a hydrolysis catalyst and water are added to the mixed solution prepared in the mixed solution preparation step, followed by hydrolysis and condensation to prepare an insulating film formation precursor.
加水分解触媒としては、酸触媒およびアルカリ触媒のいずれも用いることができるが、酸触媒を用いることが好ましい。
酸触媒としては、無機酸や有機酸を用いることができる。無機酸としては、例えば、塩酸、硝酸、硫酸、フッ酸、リン酸、ホウ酸などが挙げられる。有機酸としては、例えば、ギ酸、酢酸、プロピオン酸、シュウ酸、ｐ−トルエンスルホン酸、ベンゼンスルホン酸、メタンスルホン酸、トリフルオロ酢酸、トリクロロ酢酸などが挙げられる。
As the hydrolysis catalyst, either an acid catalyst or an alkali catalyst can be used, but an acid catalyst is preferably used.
As the acid catalyst, an inorganic acid or an organic acid can be used. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, and boric acid. Examples of the organic acid include formic acid, acetic acid, propionic acid, oxalic acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trichloroacetic acid and the like.
アルカリ触媒としては、無機塩基や有機塩基を用いることができる。
無機塩基としては、例えば、アンモニア、水酸化ナトリウム、水酸化カリウム、水酸化バリウム、水酸化カルシウムなどが挙げられる。
有機塩基としては、例えば、メタノールアミン、エタノールアミン、プロパノールアミン、ブタノールアミンなどのアルカノールアミン類、これらのアルカノールアミン類の各種Ｎ置換体、メトキシメチルアミン、メトキシエチルアミン、メトキシプロピルアミン、メトキシブチルアミン、エトキシメチルアミン、エトキシエチルアミン、エトキシプロピルアミン、エトキシブチルアミンなどのアルコキシアルキルアミン類などが挙げられる。
これらの加水分解触媒は、単独で用いても、２種以上を組み合わせて用いてもよい。
An inorganic base or an organic base can be used as the alkali catalyst.
Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.
Examples of the organic base include alkanolamines such as methanolamine, ethanolamine, propanolamine, butanolamine, various N-substituted products of these alkanolamines, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxy Examples include alkoxyalkylamines such as methylamine, ethoxyethylamine, ethoxypropylamine, and ethoxybutylamine.
These hydrolysis catalysts may be used alone or in combination of two or more.
加水分解触媒の量は、アルコキシシラン化合物中の全アルコキシル基１モルに対して、例えば、０．００００１〜０．５モルの範囲で選定される。
また、水の量は、原料のアルコキシシラン化合物中の全アルコキシル基１モルに対して、例えば、０．１〜５モルの範囲で選定される。
The amount of the hydrolysis catalyst is selected, for example, in the range of 0.00001 to 0.5 mol with respect to 1 mol of all alkoxyl groups in the alkoxysilane compound.
Moreover, the quantity of water is selected in the range of 0.1-5 mol with respect to 1 mol of all the alkoxyl groups in the alkoxysilane compound of a raw material, for example.
混合液に加水分解触媒及び水を加えた溶液の加水分解、縮合方法としては、まず、この溶液を３０℃以下の温度、例えば、室温（例えば、２０℃）で所定時間、例えば、１時間撹拌し、この溶液を加水分解させる。 As a hydrolysis and condensation method for a solution obtained by adding a hydrolysis catalyst and water to a mixed solution, this solution is first stirred at a temperature of 30 ° C. or lower, for example, room temperature (for example, 20 ° C.) for a predetermined time, for example, 1 hour. The solution is hydrolyzed.
次に、４０℃以上の温度、例えば、５０〜７０℃で所定時間、例えば、２〜２００時間撹拌し、加水分解された溶液の縮合反応を進める。 Next, the mixture is stirred at a temperature of 40 ° C. or higher, for example, 50 to 70 ° C. for a predetermined time, for example, 2 to 200 hours, and the condensation reaction of the hydrolyzed solution proceeds.
続いて、この溶液とほぼ当量の溶媒を加える。新たに加えられる溶媒としては、前述の混合液作製工程の溶媒で挙げたものと同様のものが挙げられる。 Subsequently, an approximately equivalent solvent to this solution is added. As the solvent to be newly added, the same solvents as those mentioned in the solvent in the above-mentioned mixed liquid preparation step can be mentioned.
新たに溶媒が加えられた後、所定の温度、かつ、減圧下、例えば、３０〜９０℃で０．１ｋ〜５０ｋＰａ（０．００１〜０．５ｂａｒ）の条件でさらに縮合反応を進めるとともに、加水分解に使用した水や一部の加水分解触媒や溶媒を除去する。また、比較的減圧度が高い場合は、温度を実質的に３０℃以下とすることも可能で、この場合、縮合反応の進行を抑制しながら除去することができる。これにより、絶縁膜形成前駆体が形成される。 After a new solvent is added, the condensation reaction is further advanced at a predetermined temperature and under reduced pressure, for example, at 30 to 90 ° C. under the conditions of 0.1 to 50 kPa (0.001 to 0.5 bar). Remove water and some hydrolysis catalyst and solvent used for decomposition. Further, when the degree of vacuum is relatively high, the temperature can be substantially 30 ° C. or less, and in this case, it can be removed while suppressing the progress of the condensation reaction. Thereby, an insulating film forming precursor is formed.
塗布液作製工程では、形成された絶縁膜形成前駆体を、好ましくは、ｐＨ７前後に調整した後、前述のように、例えば、固形分濃度が０．５〜５０ｗｔ％程度となるように溶媒を留去または添加する。これにより、塗布液が作製される。 In the coating liquid preparation step, after the formed insulating film forming precursor is preferably adjusted to around pH 7, as described above, for example, a solvent is added so that the solid content concentration is about 0.5 to 50 wt%. Evaporate or add. Thereby, a coating liquid is produced.
なお、塗布液の作製方法では、アルコキシシラン化合物として炭素数１個のアルコキシル基を有するアルコキシシラン化合物を用いてもよい。この場合、アルコキシシラン化合物を３０モル％以下の割合で使用するか、若しくは、炭素数２個以上のアルコール系の溶媒を使用し、アルコキシル基置換反応を行うことにより、結果的に炭素数２〜６個のアルコキシシラン化合物としてもよい。このような溶剤としては、アルコキシル基と置換反応が可能な溶剤であって、その炭素数がアルコキシシラン化合物の炭素数と同数若しくはこれより多い溶剤が用いられる。 In the method for preparing the coating solution, an alkoxysilane compound having an alkoxyl group having 1 carbon atom may be used as the alkoxysilane compound. In this case, the alkoxysilane compound is used in a proportion of 30 mol% or less, or an alcohol solvent having 2 or more carbon atoms is used to perform an alkoxyl group substitution reaction, resulting in 2 to 2 carbon atoms. It is good also as six alkoxysilane compounds. As such a solvent, a solvent capable of undergoing a substitution reaction with an alkoxyl group and having a carbon number equal to or larger than that of the alkoxysilane compound is used.
（素子分離層用薄膜、素子分離層用薄膜の形成方法、基板、および、基板の形成方法）
次に、素子分離層用薄膜、素子分離層用薄膜の形成方法、基板、および、基板の形成方法について説明する。本発明の薄膜、薄膜の形成方法、基板、および、基板の形成方法では、スピンコートなどの所定の塗布方法により、凹状の溝（トレンチ溝）が形成された基板上に、本発明の素子分離材料用塗布液からなる塗膜を形成し、この塗膜を乾燥、焼成処理することにより、素子分離層（薄膜）および薄膜を有する基板を形成する。
(Element isolation layer thin film, element isolation layer thin film formation method, substrate, and substrate formation method)
Next, the element isolation layer thin film, the element isolation layer thin film formation method, the substrate, and the substrate formation method will be described. In the thin film, the thin film forming method, the substrate, and the substrate forming method of the present invention, the element isolation of the present invention is formed on the substrate on which the concave groove (trench groove) is formed by a predetermined coating method such as spin coating. A coating film made of a coating solution for materials is formed, and this coating film is dried and baked to form a device separation layer (thin film) and a substrate having a thin film.
まず、基板上に、所定の塗布方法により本発明の素子分離材料用塗布液を塗布し、素子分離材料用塗布液からなる塗膜を形成する。所定の塗布方法としては、ディップコート法、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法などの方法が挙げられる。 First, the coating liquid for element isolation materials of this invention is apply | coated by the predetermined apply | coating method on a board | substrate, and the coating film which consists of a coating liquid for element isolation materials is formed. Examples of the predetermined coating method include dip coating, spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
ここで、基板には、その表面にトレンチ溝（凹状の溝）が形成されており（図２参照）、塗膜がトレンチ溝を埋めるとともに基板の表面を覆うように形成される。このときのトレンチ溝は、深さは２μｍ以下、Ｌｉｎｅ／Ｓｐａｃｅ＝０．０１〜５０μｍ／０．０１〜５０μｍである。なお、基板としては、例えば、シリコンウエハ、ＳｉＯ２ウエハ、ＳｉＮウエハなどの半導体基板、ガラス基板、ガラスセラミックス基板、金属基板などが挙げられる。 Here, a trench groove (concave groove) is formed on the surface of the substrate (see FIG. 2), and the coating film is formed so as to fill the trench groove and cover the surface of the substrate. The trench groove at this time has a depth of 2 μm or less and Line / Space = 0.01 to 50 μm / 0.01 to 50 μm. Examples of the substrate include semiconductor substrates such as silicon wafers, SiO 2 wafers, and SiN wafers, glass substrates, glass ceramic substrates, and metal substrates.
次に、塗膜が形成された基板を、例えば、加熱雰囲気下で乾燥し、塗膜中の溶媒を除去する。ここで、塗膜中の絶縁膜形成前駆体が炭素数２〜６個のアルコキシル基を有するので、乾燥処理において、絶縁膜形成前駆体分子の運動が容易になる。これにより、塗膜（薄膜）表面の平坦度が向上する。 Next, the substrate on which the coating film is formed is dried, for example, in a heated atmosphere, and the solvent in the coating film is removed. Here, since the insulating film formation precursor in a coating film has a C2-C6 alkoxyl group, a movement of an insulating film formation precursor molecule | numerator becomes easy in a drying process. Thereby, the flatness of the coating film (thin film) surface is improved.
乾燥温度は、８０〜２００℃であることが好ましく、１００〜１７０℃であることがさらに好ましい。また、乾燥時間は、乾燥雰囲気中の物質の種類などによって異なるが、例えば、０．５分〜１時間程度である。 The drying temperature is preferably 80 to 200 ° C, more preferably 100 to 170 ° C. Moreover, although drying time changes with kinds etc. of the substance in dry atmosphere, it is about 0.5 minute-1 hour, for example.
続いて、乾燥された薄膜を焼成し、絶縁膜形成前駆体のアルコキシド、他の有機置換基を分解除去し、ＳｉＯ２を主とする素子分離層用薄膜を形成する。ここで、塗膜中の絶縁膜形成前駆体が炭素数２〜６個のアルコキシル基を有するので、焼成処理において、絶縁膜形成前駆体分子の運動が容易になる。これにより、塗膜（薄膜）表面の平坦度が向上する。また、置換基の分解、収縮が起こる際に、骨格が固定化するタイミングが遅くなり、結果として、収縮に伴う応力が緩和され、クラック等が発生し難くなる。さらに、アルコキシル基が分解された際に、その末端が活性状態になるため、塗膜（薄膜）と基板との相互作用若しくは結合を形成し、薄膜と基板との密着性が向上する。 Subsequently, the dried thin film is baked to decompose and remove the alkoxide of the insulating film formation precursor and other organic substituents, thereby forming a thin film for an element isolation layer mainly composed of SiO 2 . Here, since the insulating film formation precursor in a coating film has a C2-C6 alkoxyl group, a movement of an insulating film formation precursor molecule | numerator becomes easy in a baking process. Thereby, the flatness of the coating film (thin film) surface is improved. In addition, when the substituent is decomposed or contracted, the timing at which the skeleton is immobilized is delayed. As a result, the stress accompanying the contraction is relieved and cracks and the like are hardly generated. Furthermore, when the alkoxyl group is decomposed, the end thereof becomes active, so that an interaction or bond between the coating film (thin film) and the substrate is formed, and the adhesion between the thin film and the substrate is improved.
焼成処理は、加熱雰囲気として、大気下、窒素雰囲気、アルゴン雰囲気、真空下、酸素濃度をコントロールした減圧下などで行うことができる。焼成温度は、３００〜１０００℃であることが好ましい。焼成時間は、焼成雰囲気中の物質の種類などによって異なるが、例えば、１５分〜１０時間程度である。これにより、基板上に薄膜が形成され、トレンチ構造内に薄膜が形成されたＳＴＩ構造を有する基板が形成される。 The firing treatment can be performed as a heating atmosphere in the air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with a controlled oxygen concentration, or the like. The firing temperature is preferably 300 to 1000 ° C. The firing time varies depending on the type of substance in the firing atmosphere, but is, for example, about 15 minutes to 10 hours. Thereby, a thin film is formed on the substrate, and a substrate having an STI structure in which the thin film is formed in the trench structure is formed.
次に、実施例および比較例を挙げ、本発明をさらに詳しく説明する。なお、以下の実施例は、本発明の好適な例を示すものであり、本発明がこれらに限定されるものではない。 Next, an Example and a comparative example are given and this invention is demonstrated in more detail. The following examples show suitable examples of the present invention, and the present invention is not limited to these examples.
（実施例１）
（１）塗布液の調製
メチルトリエトキシシラン（ＭＴＥＳ）２４．８４ｇとテトラエトキシシラン（ＴＥＯＳ）６５．５９ｇとエタノール（ＥｔＯＨ）４２．８８ｇとの混合液に、硝酸５．１１ｇと水（Ｈ２Ｏ）１２．６０ｇとを添加して、室温で１時間撹拌を行った後、７０℃で６７時間撹拌を行って加水分解・重縮合した。次に、この溶液に等量のメチルイソブチルケトン（ＭＩＢＫ）を加え、８０℃、８．８ｋＰａ（８８ｍｂａｒ）の条件でさらに重縮合反応を進めるとともに、水、溶媒を適当量留去した。最後に、プロピレングリコールモノメチルエーテル（ＰＧＭ）とＭＩＢＫを添加して、固形成分濃度１７ｗｔ％の絶縁膜形成前駆体を含む塗布液Ａを調製した。
Example 1
(1) Preparation of coating solution To a mixed solution of 24.84 g of methyltriethoxysilane (MTES), 65.59 g of tetraethoxysilane (TEOS) and 42.88 g of ethanol (EtOH), 5.11 g of nitric acid and water (H 2 O) 12.60 g was added and stirred at room temperature for 1 hour, and then stirred at 70 ° C. for 67 hours for hydrolysis and polycondensation. Next, an equal amount of methyl isobutyl ketone (MIBK) was added to this solution, and the polycondensation reaction was further carried out under the conditions of 80 ° C. and 8.8 kPa (88 mbar), and appropriate amounts of water and solvent were distilled off. Finally, propylene glycol monomethyl ether (PGM) and MIBK were added to prepare a coating liquid A containing an insulating film forming precursor having a solid component concentration of 17 wt%.
（２）絶縁膜形成前駆体の構造
この塗布液Ａをスピンコート法によりノンドープＳｉウエハ上に塗布し、１２０℃で１．５分間の乾燥を行って塗布液中に含まれる縮合物のＦＴ−ＩＲスペクトルを確認した。この結果を図１に示す。図１に示すように、波数２９００ｃｍ−１付近にエトキシ基に帰属されるＣ−Ｈのピークを確認した。このため、絶縁膜形成前駆体には、その分子の末端に炭素数２〜６個のアルコキシル基（エトキシ基）を有していることを確認した。
(2) Structure of Insulating Film Forming Precursor This coating solution A is applied onto a non-doped Si wafer by a spin coating method, dried at 120 ° C. for 1.5 minutes, and FT− of the condensate contained in the coating solution. An IR spectrum was confirmed. The result is shown in FIG. As shown in FIG. 1, a C—H peak attributed to an ethoxy group was confirmed in the vicinity of a wave number of 2900 cm −1 . For this reason, it was confirmed that the insulating film forming precursor has an alkoxyl group (ethoxy group) having 2 to 6 carbon atoms at the end of the molecule.
（３）ラインパターンに対する埋め込み性
図２に示すようなＬｉｎｅ／Ｓｐａｃｅ＝０．２５μｍ／０．５μｍ、段差：０．５μｍのラインパターンを持ったＳｉウエハ上に塗布液Ａをスピンコート法により塗布した。この塗布膜は、石英チューブを取り付けた赤外線加熱炉（アルバック理工社製：ＲＨＬ−Ｅ４１６）にて、Ｎ２／Ｏ２＝４／１雰囲気中で１２０℃、５分間の加熱をした後、Ｎ２減圧下で４００℃まで５℃／ｍｉｎ、更に９００℃まで５℃／ｍｉｎで昇温を行い、２時間保持した。そして、Ｈ２Ｏ／Ｏ２＝１／９雰囲気で９００℃、１時間処理を行って絶縁膜を形成した。絶縁膜が形成されたＳｉウエハを切断し、切断面を走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察したところ、図３に示すように、Ｓｉウエハ（基板）上に平坦な絶縁膜（薄膜）が形成されていることを確認した。また、Ｓｉウエハのラインパターンに対して隙間がなく絶縁膜が埋め込まれていることを確認した。
(3) Embeddability with respect to line pattern As shown in FIG. 2, the coating liquid A is applied onto a Si wafer having a line pattern of Line / Space = 0.25 μm / 0.5 μm and step: 0.5 μm by spin coating. did. This coating film was heated at 120 ° C. for 5 minutes in an N 2 / O 2 = 4/1 atmosphere in an infrared heating furnace (RUL-E416, manufactured by ULVAC-RIKO, Inc.) attached with a quartz tube. 2 The temperature was raised to 400 ° C. under reduced pressure at 5 ° C./min, and further to 900 ° C. at 5 ° C./min, and held for 2 hours. Then, an insulating film was formed by performing treatment at 900 ° C. for 1 hour in an atmosphere of H 2 O / O 2 = 1/9. When the Si wafer on which the insulating film was formed was cut and the cut surface was observed with a scanning electron microscope (FE-SEM), a flat insulating film (thin film) was formed on the Si wafer (substrate) as shown in FIG. It was confirmed that it was formed. Further, it was confirmed that there was no gap with respect to the line pattern of the Si wafer and the insulating film was embedded.
（４）電気的特性
ｐ型低抵抗Ｓｉウエハ（抵抗率：０．０２Ω・ｃｍ以下）上に塗布液Ａをスピンコート法により塗布し、前述と同様の方法で焼成を行い、絶縁膜を形成した。形成された絶縁膜の膜厚は２１３ｎｍであった。絶縁膜表面並びにＳｉウエハ裏面にアルミを蒸着してＭＩＭ構造キャパシタを作製し、電気的特性を評価した。絶縁膜表面にはマスクを介して、φ＝１００、２５０、５００、１０００μｍの上部電極を形成した。誘電率は容量―電圧（Ｃ−Ｖ）測定より算出し、３．６１であった。また、図４に示すように、電流―電圧（Ｉ―Ｖ）測定からリーク電流は１ＭＶ／ｃｍで２×１０−１０Ａ／ｃｍ２、５ＭＶ／ｃｍで３×１０−８Ａ／ｃｍ２であり、絶縁破壊強度（印加電圧を変化させ、瞬間に多量のリーク電流が生じたときの値）は７ＭＶ／ｃｍであった。
(4) Electrical characteristics Coating liquid A is applied onto a p-type low-resistance Si wafer (resistivity: 0.02 Ω · cm or less) by spin coating, and baked by the same method as described above to form an insulating film. did. The film thickness of the formed insulating film was 213 nm. MIM structure capacitors were fabricated by evaporating aluminum on the insulating film surface and the back surface of the Si wafer, and the electrical characteristics were evaluated. Upper electrodes of φ = 100, 250, 500, and 1000 μm were formed on the surface of the insulating film through a mask. The dielectric constant was calculated from capacitance-voltage (C-V) measurement and found to be 3.61. Further, as shown in FIG. 4, the leakage current is 2 × 10 −10 A / cm 2 at 1 MV / cm and 3 × 10 −8 A / cm 2 at 5 MV / cm as measured by current-voltage (IV). In addition, the dielectric breakdown strength (value when a large amount of leakage current was generated instantaneously when the applied voltage was changed) was 7 MV / cm.
なお、Ｃ−Ｖ測定には、アジレント・テクノロジー社製Ａｇｉｌｅｎｔ４２９４Ａプレシジョン・インピーダンス・アナライザ、カスケードマイクロテック社製ＭＩＣＲＯＣＨＡＭＢＥＲ付きマニュアルプローバを用いた。測定条件は以下の通りである。
OSC FREQ:300kHz、
OSC LEVEL:500mVolt、
BIAS:-40〜40V
For CV measurement, Agilent 4294A Precision Impedance Analyzer manufactured by Agilent Technologies and a manual prober with MICROCHAMBER manufactured by Cascade Microtech were used. The measurement conditions are as follows.
OSC FREQ: 300kHz,
OSC LEVEL: 500mVolt,
BIAS: -40 ~ 40V
Ｉ−Ｖ測定にはアジレント・テクノロジー社製Ａｇｉｌｅｎｔ４１５６Ｃプレシジョン半導体パラメータ・アナライザ、アジレント・テクノロジー社製Ａｇｉｌｅｎｔ４１５０１Ｂ ＳＭＵ/パルス・ジェネレータ・エクスパンダ、カスケードマイクロテック社製ＭＩＣＲＯＣＨＡＭＢＥＲ付きマニュアルプローバを用いた。測定条件は以下の通りである。
ＳＴＡＲＴ：０Ｖ、
ＳＴＯＰ：−２００Ｖ、
ＳＴＥＰ：−１Ｖ
For the IV measurement, an Agilent 4156C precision semiconductor parameter analyzer manufactured by Agilent Technologies, an Agilent 41501B SMU / pulse generator expander manufactured by Agilent Technologies, and a manual prober with MICROCHAMBER manufactured by Cascade Microtech Co., Ltd. were used. The measurement conditions are as follows.
START: 0V
STOP: -200V
STEP: -1V
（実施例２）
メチルｎ−プロポキシシラン（ＭＴｎＰＳ）３０．５６ｇとテトラｎ−プロポキシシラン（ＴｎＰＯＳ）８１．６０ｇ、１−プロパノール（ＮＰＡ）２０．１６ｇの混合液に硝酸５．１７ｇと水１２．５１ｇを添加して室温で１時間撹拌を行った後、５０℃で１４０時間撹拌を行って加水分解・重縮合した。その他は実施例１と同様の手順で、固形成分濃度１９．３ｗｔ％の絶縁膜形成前駆体を含む塗布液Ｂを得た。この塗布液Ｂ中に含まれる縮合物中に含まれる縮合物のＦＴ−ＩＲスペクトルを確認したところ、２９００ｃｍ−１付近にｎ―プロポキシ基に帰属されるＣ−Ｈのピークを確認した。このため、絶縁膜形成前駆体には、その分子の末端に炭素数２〜６個のアルコキシル基（ｎ―プロポキシ基）を有していることを確認した。
(Example 2)
To a mixed solution of 30.56 g of methyl n-propoxysilane (MTnPS), 81.60 g of tetra n-propoxysilane (TnPOS) and 20.16 g of 1-propanol (NPA), 5.17 g of nitric acid and 12.51 g of water were added. After stirring at room temperature for 1 hour, the mixture was stirred at 50 ° C. for 140 hours for hydrolysis and polycondensation. Others were the same procedures as in Example 1 to obtain a coating solution B containing an insulating film forming precursor having a solid component concentration of 19.3 wt%. When the FT-IR spectrum of the condensate contained in the condensate contained in this coating liquid B was confirmed, the C—H peak attributed to the n-propoxy group was confirmed in the vicinity of 2900 cm −1 . For this reason, it was confirmed that the insulating film forming precursor had an alkoxyl group having 2 to 6 carbon atoms (n-propoxy group) at the end of the molecule.
塗布液Ｂに関しても、実施例１と同様にラインパターンに対する埋め込み性や電気的特性を評価した。ラインパターン上に成膜した断面をＦＥ−ＳＥＭで観察したところ、Ｓｉウエハ上に平坦な絶縁膜が形成されていることを確認した。また、ラインパターンに対して隙間がなく絶縁膜が埋め込まれていた。形成された絶縁膜の膜厚は２２０ｎｍであり、誘電率は３．５３、リーク電流は１ＭＶ／ｃｍで１×１０−１０Ａ／ｃｍ２、５ＭＶ／ｃｍで２×１０−７Ａ／ｃｍ２、絶縁破壊強度は７ＭＶ／ｃｍであった。 Regarding the coating liquid B, the embedding property and the electrical characteristics with respect to the line pattern were evaluated in the same manner as in Example 1. When the cross section formed on the line pattern was observed with an FE-SEM, it was confirmed that a flat insulating film was formed on the Si wafer. Further, there is no gap with respect to the line pattern, and the insulating film is embedded. The formed insulating film has a thickness of 220 nm, a dielectric constant of 3.53, a leakage current of 1 × 10 −10 A / cm 2 at 1 MV / cm, and 2 × 10 −7 A / cm 2 at 5 MV / cm. The dielectric breakdown strength was 7 MV / cm.
（実施例３）
ＭＴＥＳ ５６．０６ｇとＴＥＯＳ ３１．３６ｇ、ＥｔＯＨ ４４．３７ｇの混合液に硝酸５．１０ｇと水１３．１１ｇを添加して室温で１時間撹拌を行った後、５０℃で４８時間撹拌を行って加水分解・重縮合した。その他は実施例１と同様の手順で、固形成分濃度１４ｗｔ％の絶縁膜形成前駆体を含む塗布液Ｃを得た。この塗布液Ｃ中に含まれる縮合物のＦＴ−ＩＲスペクトルを確認したところ、２９００ｃｍ−１付近にエトキシ基に帰属されるＣ−Ｈのピークを確認した。このため、絶縁膜形成前駆体には、その分子の末端に炭素数２〜６個のアルコキシル基（エトキシ基）を有していることを確認した。
(Example 3)
After adding 5.10 g of nitric acid and 13.11 g of water to a mixed solution of 56.06 g of MTES, 31.36 g of TEOS, and 44.37 g of EtOH, the mixture was stirred at room temperature for 1 hour, and then stirred at 50 ° C. for 48 hours. Hydrolyzed and polycondensed. Others were the same procedures as in Example 1 to obtain a coating liquid C containing an insulating film forming precursor having a solid component concentration of 14 wt%. When the FT-IR spectrum of the condensate contained in this coating liquid C was confirmed, the C—H peak attributed to the ethoxy group was confirmed in the vicinity of 2900 cm −1 . For this reason, it was confirmed that the insulating film forming precursor has an alkoxyl group (ethoxy group) having 2 to 6 carbon atoms at the end of the molecule.
塗布液Ｃに関しても、実施例１と同様にラインパターンに対する埋め込み性や電気的特性を評価した。ラインパターン上に成膜した断面をＦＥ−ＳＥＭで観察したところ、Ｓｉウエハ上に平坦な絶縁膜が形成されていることを確認した。また、ラインパターンに対して隙間がなく絶縁膜が埋め込まれていた。形成された絶縁膜の膜厚は２０６ｎｍであり、誘電率は３．６９、リーク電流は１ＭＶ／ｃｍで１×１０−１０Ａ／ｃｍ２、５ＭＶ／ｃｍで３×１０−８Ａ／ｃｍ２、絶縁破壊強度は７ＭＶ／ｃｍであった。 With respect to the coating liquid C as well, the embedding property and electrical characteristics with respect to the line pattern were evaluated in the same manner as in Example 1. When the cross section formed on the line pattern was observed with an FE-SEM, it was confirmed that a flat insulating film was formed on the Si wafer. Further, there is no gap with respect to the line pattern, and the insulating film is embedded. The formed insulating film has a thickness of 206 nm, a dielectric constant of 3.69, a leakage current of 1 × 10 −10 A / cm 2 at 1 MV / cm, and 3 × 10 −8 A / cm 2 at 5 MV / cm. The dielectric breakdown strength was 7 MV / cm.
（比較例１）
ＭＴＭＳ １６．２９ｇとＴＥＯＳ ５５．４４ｇをＩＰＡ １８．９０ｇに加えて室温で１５分間撹拌を行った後、０．１Ｎ硝酸４．８２ｇと水４６．４４ｇ、ＩＰＡ ８．１０ｇを添加して３０℃で２４時間撹拌を行って加水分解・重縮合した。ＰＧＭとＭＩＢＫを添加して、固形成分濃度１３ｗｔ％の絶縁膜形成縮合物を含む塗布液Ｄを調製した。実施例１と同様の手順で塗布液Ｄ中に含まれる縮合物のＦＴ−ＩＲスペクトルを確認した。この結果を図５に示す。図５に示すように、２９００ｃｍ−１付近でアルコキシル基に帰属されるＣ−Ｈのピークが観察されず、一方、３４００ｃｍ−１付近で物理的に吸着したＨ２Ｏに帰属される強いピークが見られた。
(Comparative Example 1)
After adding 16.29 g of MTMS and 55.44 g of TEOS to 18.90 g of IPA and stirring at room temperature for 15 minutes, 4.82 g of 0.1N nitric acid, 46.44 g of water and 8.10 g of IPA were added and 30 ° C. And then hydrolyzed and polycondensed by stirring for 24 hours. PGM and MIBK were added to prepare a coating liquid D containing an insulating film forming condensate having a solid component concentration of 13 wt%. The FT-IR spectrum of the condensate contained in the coating liquid D was confirmed by the same procedure as in Example 1. The result is shown in FIG. As shown in FIG. 5, is not the peak of C-H attributable to an alkoxyl group at around 2900 cm -1 was observed, whereas, a strong peak attributed in H 2 O was physically adsorbed around 3400 cm -1 It was seen.
塗布液Ｄに関しても、実施例１と同様にラインパターンに対する埋め込み性や電気的特性を評価した。図６に示すように、ラインパターン上に成膜した断面をＦＥ−ＳＥＭで観察したところ、Ｓｉウエハ上に平坦な絶縁膜が形成されていたが、ラインパターンと絶縁膜との間に隙間が見られた。形成された絶縁膜の膜厚は１６７ｎｍであり、誘電率は３．７４、リーク電流は１ＭＶ／ｃｍで５×１０−１０Ａ／ｃｍ２、５ＭＶ／ｃｍで８×１０−９Ａ／ｃｍ２、絶縁破壊強度は７ＭＶ／ｃｍであった。 Regarding the coating solution D, the embedding property with respect to the line pattern and the electrical characteristics were evaluated in the same manner as in Example 1. As shown in FIG. 6, when the cross section formed on the line pattern was observed with an FE-SEM, a flat insulating film was formed on the Si wafer, but there was a gap between the line pattern and the insulating film. It was seen. The formed insulating film has a thickness of 167 nm, a dielectric constant of 3.74, a leakage current of 5 × 10 −10 A / cm 2 at 1 MV / cm, and 8 × 10 −9 A / cm 2 at 5 MV / cm. The dielectric breakdown strength was 7 MV / cm.
（比較例２）
メチルトリメトキシシラン（ＭＴＭＳ）１９．６２ｇとテトラメトキシシラン（ＴＭＯＳ）４８．８０ｇ、ＭｅＯＨ ６３．２７ｇの混合液に硝酸５．２８ｇと水１３．０３ｇを添加して室温で１時間撹拌を行った後、５０℃で７２時間撹拌を行って加水分解・重縮合した。その他は実施例１と同様の手順で、固形成分濃度１５ｗｔ％の絶縁膜形成縮合物を含む塗布液Ｅを得た。この塗布液Ｅ中に含まれる縮合物のＦＴ−ＩＲスペクトルを確認したところ、２９００ｃｍ−１付近にメトキシ基に帰属されるＣ−Ｈのピークが観察された。
(Comparative Example 2)
5.28 g of nitric acid and 13.03 g of water were added to a mixture of 19.62 g of methyltrimethoxysilane (MTMS), 48.80 g of tetramethoxysilane (TMOS) and 63.27 g of MeOH, and the mixture was stirred at room temperature for 1 hour. Then, it stirred for 72 hours at 50 degreeC, and hydrolyzed and polycondensed. Others were the same procedures as in Example 1 to obtain a coating solution E containing an insulating film forming condensate having a solid component concentration of 15 wt%. When the FT-IR spectrum of the condensate contained in this coating liquid E was confirmed, the C—H peak attributed to the methoxy group was observed in the vicinity of 2900 cm −1 .
塗布液Ｅに関しても、実施例１と同様にラインパターンに対する埋め込み性や電気的特性を評価した。ラインパターン上に成膜した断面をＦＥ−ＳＥＭで観察したところ、Ｓｉウエハ上に平坦な絶縁膜が形成されていたが、ラインパターンと絶縁膜との間に隙間が見られた。形成された絶縁膜の膜厚は２０３ｎｍであり、誘電率は３．６８、リーク電流は１ＭＶ／ｃｍで１×１０−１０Ａ／ｃｍ２、５ＭＶ／ｃｍで２×１０−８Ａ／ｃｍ２、絶縁破壊強度は７ＭＶ／ｃｍであった。 Regarding the coating liquid E, the embedding property and the electrical characteristics with respect to the line pattern were evaluated in the same manner as in Example 1. When a cross-section formed on the line pattern was observed with an FE-SEM, a flat insulating film was formed on the Si wafer, but a gap was observed between the line pattern and the insulating film. The formed insulating film has a thickness of 203 nm, a dielectric constant of 3.68, a leakage current of 1 × 10 −10 A / cm 2 at 1 MV / cm, and 2 × 10 −8 A / cm 2 at 5 MV / cm. The dielectric breakdown strength was 7 MV / cm.
これらの結果を表１に示す。
表１に示すように、分子の末端官能基にエトキシ基、ｎ―プロポキシ基を有することにより、Ｓｉウエハ上に平坦な絶縁膜が形成され、ラインパターンに対して隙間がなく絶縁膜が埋め込まれていることが確認できた。 As shown in Table 1, since the terminal functional group of the molecule has an ethoxy group and an n-propoxy group, a flat insulating film is formed on the Si wafer, and the insulating film is embedded without a gap with respect to the line pattern. It was confirmed that
また、分子の末端官能基にイソプロポキシ基、ｎ−ブトキシ基、ペントキシ基、ヘキソキシ基を有する場合について、同様の手順でＳｉウエハ上に絶縁膜を形成したところ、Ｓｉウエハ上に平坦な絶縁膜が形成され、ラインパターンに対して隙間がなく絶縁膜が埋め込まれていることが確認できた。 In addition, when the terminal functional group of the molecule has an isopropoxy group, n-butoxy group, pentoxy group, and hexoxy group, when an insulating film is formed on the Si wafer in the same procedure, a flat insulating film is formed on the Si wafer. It was confirmed that the insulating film was embedded without gaps in the line pattern.
このため、分子の末端官能基に炭素数２〜６個のアルコキシル基を有することにより、基板上に平坦な薄膜が形成され、ラインパターンに対して隙間がなく薄膜が埋め込まれていることが確認できた。したがって、基板と素子分離層との剥離やクラックが発生し難く、凹状の溝を有する基板上に平坦な素子分離層を形成することができる。また、ＣＭＰレス工程で溝内部にシリコン酸化膜を形成することができる。 For this reason, it is confirmed that by having an alkoxyl group having 2 to 6 carbon atoms in the terminal functional group of the molecule, a flat thin film is formed on the substrate, and there is no gap with respect to the line pattern and the thin film is embedded. did it. Therefore, peeling and cracking between the substrate and the element isolation layer hardly occur, and a flat element isolation layer can be formed on the substrate having a concave groove. In addition, a silicon oxide film can be formed inside the trench by a CMP-less process.
Claims (9)
アルコキシシラン化合物が加水分解、縮合された絶縁膜形成前駆体と、
前記絶縁膜形成前駆体の濃度を所望の濃度に調製する溶媒と、を備え、
前記絶縁膜形成前駆体は、（Ｓｉ−Ｏ）の繰り返し単位を主骨格としたポリマーであり、その分子の末端に炭素数２〜６個のアルコキシル基を有している、ことを特徴とする素子分離材料用塗布液。 An element isolation material coating liquid used for forming an element isolation layer of a shallow trench isolation structure of a semiconductor device,
An insulating film forming precursor in which an alkoxysilane compound is hydrolyzed and condensed;
A solvent for adjusting the concentration of the insulating film forming precursor to a desired concentration, and
The insulating film forming precursor is a polymer having a repeating unit of (Si—O) as a main skeleton, and has an alkoxyl group having 2 to 6 carbon atoms at the end of the molecule. Coating liquid for element isolation material.
Ｓｉ（ＯＲ１）４（Ｒ１は炭素数２〜６個の有機基を示す。）で表される第１のアルコキシシラン化合物と、
Ｒ２ ｎＳｉ（ＯＲ３）４−ｎ（Ｒ２はメチル基、エチル基、プロピル基、ビニル基、または、フェニル基を示す。Ｒ３は炭素数２〜６個の有機基を示す。ｎは１〜３の整数である。）で表される第２のアルコキシシラン化合物と、
が、混合されている、ことを特徴とする請求項１に記載の素子分離材料用塗布液。 The alkoxysilane compound is
A first alkoxysilane compound represented by Si (OR 1 ) 4 (R 1 represents an organic group having 2 to 6 carbon atoms);
R 2 n Si (OR 3 ) 4-n (R 2 represents a methyl group, an ethyl group, a propyl group, a vinyl group, or a phenyl group. R 3 represents an organic group having 2 to 6 carbon atoms. N Is an integer of 1 to 3.) and a second alkoxysilane compound represented by
2. The element isolation material coating solution according to claim 1, wherein the element isolation material is mixed.
アルコキシシラン化合物と第１の溶媒との混合液を作製する混合液作製工程と、
前記混合液作製工程により作製された混合液を加水分解、縮合して絶縁膜形成前駆体を作製する絶縁膜形成前駆体作製工程と、
前記絶縁膜形成前駆体作製工程により作製された絶縁膜形成前駆体に第２の溶媒を加えることにより塗布液を作製する塗布液作製工程と、を備え、
前記混合液作製工程では、前記アルコキシシラン化合物に、炭素数２〜６個のアルコキシル基を有するアルコキシシラン化合物を用いる、ことを特徴とする素子分離材料用塗布液の作製方法。 A method for producing a coating liquid for an element isolation material used for forming an element isolation layer having a shallow trench isolation structure of a semiconductor device,
A mixed liquid preparation step of preparing a mixed liquid of the alkoxysilane compound and the first solvent;
An insulating film forming precursor manufacturing step of preparing an insulating film forming precursor by hydrolyzing and condensing the mixed liquid prepared by the mixed liquid manufacturing step;
A coating liquid preparation step of preparing a coating liquid by adding a second solvent to the insulating film formation precursor prepared by the insulating film formation precursor preparation step,
In the mixed liquid preparation step, an alkoxysilane compound having an alkoxyl group having 2 to 6 carbon atoms is used as the alkoxysilane compound.
Ｓｉ（ＯＲ１）４（Ｒ１は炭素数２〜６個の有機基を示す。）で表される第１のアルコキシシラン化合物と、
Ｒ２ ｎＳｉ（ＯＲ３）４−ｎ（Ｒ２はメチル基、エチル基、プロピル基、ビニル基、または、フェニル基を示す。Ｒ３は炭素数２〜６個の有機基を示す。ｎは１〜３の整数である。）で表される第２のアルコキシシラン化合物と、
の混合物を用いる、ことを特徴とする請求項３に記載の素子分離材料用塗布液の作製方法。 In the mixed liquid preparation step, the alkoxysilane compound
A first alkoxysilane compound represented by Si (OR 1 ) 4 (R 1 represents an organic group having 2 to 6 carbon atoms);
R 2 n Si (OR 3 ) 4-n (R 2 represents a methyl group, an ethyl group, a propyl group, a vinyl group, or a phenyl group. R 3 represents an organic group having 2 to 6 carbon atoms. N Is an integer of 1 to 3.) and a second alkoxysilane compound represented by
The method for producing a coating liquid for an element isolation material according to claim 3, wherein the mixture is used.
前記加水分解工程で加水分解された溶液を４０℃以上の温度で縮合反応を進める縮合反応工程と、
前記縮合反応工程で縮合反応が進められた溶液を、減圧下で前記加水分解工程で加えられた水および一部の加水分解触媒と溶媒を除去する除去工程と、
を備える、ことを特徴とする請求項３または４に記載の素子分離材料用塗布液の作製方法。 In the insulating film formation precursor preparation step, a hydrolysis step of hydrolyzing a solution obtained by adding a hydrolysis catalyst and water to the mixed solution at a temperature of 30 ° C. or less;
A condensation reaction step of advancing the condensation reaction of the solution hydrolyzed in the hydrolysis step at a temperature of 40 ° C. or higher;
A removal step of removing the water and a part of the hydrolysis catalyst and the solvent added in the hydrolysis step under reduced pressure from the solution subjected to the condensation reaction in the condensation reaction step;
The method for producing a coating liquid for an element isolation material according to claim 3 or 4, comprising:
前記塗膜形成工程により形成された塗膜中の溶媒を除去して塗膜を乾燥させる乾燥工程と、
前記乾燥工程により乾燥された塗膜を焼成して素子分離層用薄膜を形成する薄膜形成工程と、
を備える、ことを特徴とする素子分離層用薄膜の形成方法。 A coating film forming step of forming a coating film by applying the element separating material coating liquid according to claim 1 or 2,
A drying step of drying the coating film by removing the solvent in the coating film formed by the coating film forming step;
A thin film forming step of baking the coating film dried by the drying step to form a thin film for an element isolation layer;
A method for forming a thin film for an element isolation layer, comprising:
トレンチ構造を有するシリコン基板上に、請求項６に記載の素子分離層用薄膜の形成方法により形成した薄膜を有することを特徴とする基板。 A substrate having a shallow trench isolation structure,
A substrate comprising a thin film formed by the method for forming a thin film for an element isolation layer according to claim 6 on a silicon substrate having a trench structure.
トレンチ構造を有するシリコン基板上に、請求項６に記載の素子分離層用薄膜の形成方法により薄膜を形成する、ことを特徴とする基板の形成方法。 A method of forming a substrate having a shallow trench isolation structure,
A method for forming a substrate, comprising: forming a thin film on a silicon substrate having a trench structure by the method for forming a thin film for an element isolation layer according to claim 6.
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