JP2003007695A - Method for manufacturing low-dielectric porous film - Google Patents
Method for manufacturing low-dielectric porous filmInfo
- Publication number
- JP2003007695A JP2003007695A JP2001178927A JP2001178927A JP2003007695A JP 2003007695 A JP2003007695 A JP 2003007695A JP 2001178927 A JP2001178927 A JP 2001178927A JP 2001178927 A JP2001178927 A JP 2001178927A JP 2003007695 A JP2003007695 A JP 2003007695A
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- Prior art keywords
- pressure
- manufacturing
- film
- inert gas
- dielectric
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Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000011261 inert gas Substances 0.000 claims abstract description 32
- 239000004065 semiconductor Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 8
- 229910010272 inorganic material Inorganic materials 0.000 claims description 7
- 239000011147 inorganic material Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229920000620 organic polymer Polymers 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000011368 organic material Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910020177 SiOF Inorganic materials 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 19
- 239000000203 mixture Substances 0.000 abstract description 10
- 230000007704 transition Effects 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 76
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000012528 membrane Substances 0.000 description 18
- 238000005229 chemical vapour deposition Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910003472 fullerene Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 101100366711 Arabidopsis thaliana SSL13 gene Proteins 0.000 description 1
- 108700042918 BF02 Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 101100366561 Panax ginseng SS11 gene Proteins 0.000 description 1
- 101150016011 RR11 gene Proteins 0.000 description 1
- 101150048609 RR21 gene Proteins 0.000 description 1
- 101150110620 RR22 gene Proteins 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、誘電率を低下させ
た誘電膜を有する半導体チップに関し、特に表面に隙孔
を形成することで誘電率を低下させた誘電膜を有する半
導体チップに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor chip having a dielectric film whose dielectric constant is lowered, and more particularly to a semiconductor chip having a dielectric film whose dielectric constant is lowered by forming voids on its surface.
【０００２】[0002]
【従来の技術】近年、ＵＬＳＩ素子の複雑化に伴い、複
数の金属リード工程が要求されている。それにより、こ
れまでの金属リード間の絶縁に最も汎用であった誘電率
材料のＳｉＯ2（誘電率約４．１〜４．５）では、もは
や対応できなくなっている。その主原因として、内層リ
ードの間の距離が短くなるにつれて、以下の式に示すよ
うに、両リード間の容量が増加することが挙げられる。2. Description of the Related Art In recent years, a plurality of metal lead processes have been required due to the complexity of ULSI devices. As a result, SiO 2 (dielectric constant of about 4.1 to 4.5), which has been the most general-purpose material for insulation between metal leads up to now, is no longer applicable. The main reason for this is that as the distance between the inner layer leads decreases, the capacitance between the leads increases as shown in the following equation.
【０００３】[0003]
【数１】 [Equation 1]
【０００４】すなわち上記式によれば、同じ誘電率条件
において、両リード間距離（ｄ）が小さいほど容量が大
きくなるので、ＲＣ遅延時間（Ｒ：金属リード抵抗、
Ｃ：金属層間）が増加し、素子伝送速度の減衰が起こ
る。従って、チップ回路サイズを小さくするためには、
低誘電率材料（ｋ＜４．１）で容量値を制御するのが最
も直接的な方法である。That is, according to the above equation, under the same permittivity condition, the smaller the distance (d) between the leads is, the larger the capacitance becomes. Therefore, the RC delay time (R: metal lead resistance,
(C: metal layer) increases, and the device transmission speed is attenuated. Therefore, in order to reduce the chip circuit size,
The most direct method is to control the capacitance value with a low dielectric constant material (k <4.1).
【０００５】低誘電率材料は、チップ回路において導体
間の電気距離や漏話を減少させたり、結合容量を低下さ
せたりする効果があり、それにより、ＲＣ遅延時間の短
縮、伝送速度の向上、結合雑音の改善などが可能であ
る。The low dielectric constant material has the effect of reducing the electrical distance between conductors and crosstalk in the chip circuit, and also reducing the coupling capacitance, thereby shortening the RC delay time, improving the transmission speed, and coupling. It is possible to improve noise.
【０００６】これまでに、低い誘電率を有する材料がい
くつか見出されており、このような材料は、化学的には
無機低誘電率材料と有機低誘電率材料とに分類される。
無機材料は、化学蒸着（ＣＶＤ）によって、例えばフッ
素、炭素または水素を含んでもよい二酸化ケイ素からな
る膜を形成するのに用いられる。これらは従来の製造設
備をそのまま、または軽微な変更のみ施すことよって用
いることができるという利点を有する。一方、上記有機
材料は、主に回転塗布（Spin On Glass，ＳＯＧ）方法
で膜を形成するのに用いられる。誘電率を両者で比較す
ると、無機誘電率材料の誘電率変化は約２．５〜３．７
の範囲内で材料により一定である。一方、有機材料の誘
電率は結合原子の種類により常に約２〜３．７の間で変
化し、いずれも空気と同じ誘電率１．０は実現されてい
ない。Some materials having a low dielectric constant have been found so far, and such materials are chemically classified into inorganic low dielectric constant materials and organic low dielectric constant materials.
Inorganic materials are used by chemical vapor deposition (CVD) to form films of silicon dioxide, which may include, for example, fluorine, carbon or hydrogen. These have the advantage that they can be used with conventional manufacturing equipment as they are or with only minor modifications. On the other hand, the above organic material is mainly used for forming a film by a spin coating (Spin On Glass, SOG) method. Comparing the two dielectric constants, the change in the dielectric constant of the inorganic dielectric material is about 2.5 to 3.7.
It is constant depending on the material within the range. On the other hand, the dielectric constant of an organic material always changes between about 2 and 3.7 depending on the type of bonding atom, and none of them has realized the same dielectric constant of 1.0 as air.
【０００７】一方、このような材料に対してさらに、膜
形成用の溶媒を揮発させたり、膜内混合物を溶解させた
りして多孔質構造を形成させることにより、更に低い誘
電率（ｋ＜２）を実現できる。このような材料は多孔性
低誘電率材料といわれており、理想的な容量値１．０を
実現できる潜在性を秘めている。On the other hand, by further evaporating a solvent for forming a film or dissolving an in-film mixture with respect to such a material to form a porous structure, a lower dielectric constant (k <2) is obtained. ) Can be realized. Such a material is said to be a porous low dielectric constant material and has the potential to realize an ideal capacitance value of 1.0.
【０００８】例えば、米国特許第５，４７０，８０２
号、米国特許第５，４９４，８５８号、米国特許第５，
１０３，２８８号、米国特許第５，５４８，１５９号、
米国特許第５，５６１，３１８号、米国特許第５，５６
９，０５８号、米国特許第５，６６１，３４４号、米国
特許第５，７４７，８８０号、米国特許第５，７５０，
４１５号、米国特許第５，８０４，５０８号に、このよ
うな多孔性低誘電率材料の製造方法が開示されている。For example, US Pat. No. 5,470,802
U.S. Pat. No. 5,494,858, U.S. Pat. No. 5,
103,288, US Pat. No. 5,548,159,
US Pat. No. 5,561,318, US Pat. No. 5,56
9,058, US Patent No. 5,661,344, US Patent No. 5,747,880, US Patent No. 5,750,
No. 415, U.S. Pat. No. 5,804,508 discloses a method for producing such a porous low dielectric constant material.
【０００９】具体的には、異なる揮発度の溶媒を膜から
揮発させてなる多孔質膜の形成方法が挙げられる。例え
ば米国特許第５，４９４，８５８号によれば、先ず１：
３：１：０．０００７のモル比で、テトラエチルオルト
シリケート（ＴＥＯＳ）、Ｃ 2Ｈ5ＯＨ、Ｈ2ＯおよびＨ
Ｃｌを、６０℃で１．５時間攪拌混合し、得られた溶液
に０．０５Ｍ ＮＨ4ＯＨを加えた後、直ちに回転塗布
機で溶液をチップに塗布し、ＮＨ4ＯＨの添加は溶液の
ゲル化率を加速し、ここで一般的にＮＨ4ＯＨの添加率
は溶液体積の１／１０であり、ゲル膜を塗布したチップ
を３７℃で飽和エタノールガスを含む大気中に２４時間
置き、膜を成熟（aging）させた後、圧力変化により膜
内の溶媒を除去し、多孔質膜を形成する方法が記載され
ている。この際、工程中の圧力は１大気圧以下であり、
溶媒を液体から気体に変える、すなわち溶媒の超臨界状
態または超臨界条件に近い高圧下において、溶媒を圧縮
ガスにして除去することによって孔洞を形成する。これ
らの工程はいずれも、慎重な制御を必要とし、膜が過剰
収縮する現象（shrinkage effect）を避けなければなら
ない。上記方法で得られた膜の多孔質の体積率、直径、
分布は、反応条件、溶媒の種類により多様であるが、一
般的に、膜中の多孔質の体積は約２０％〜９５％、好ま
しくは７５％以上であり、平均直径は約８０ｎｍ以下、
好ましくは２ｎｍ〜２５ｎｍであり、多孔質が体積の８
０％を占める場合、材料誘電率は約１．５以下である。
ここで、膜中の多孔質の占有体積率が大きいほど、表面
接着および耐熱処理特性が劣る。従って、その後のチッ
プ処理工程に耐えうるように、通常、多孔質膜の上下層
に、ＣＶＤにより接着層が設けられる。このような層に
よって接着効果が増強され、さらに多孔質内への材料の
吸水または原子の遷移滲出を阻止する効果がある。Specifically, solvents of different volatility are removed from the membrane.
A method for forming a porous film formed by volatilization may be mentioned. example
For example, according to US Pat. No. 5,494,858, first:
Tetraethyl ortho at a molar ratio of 3: 1: 0.0007.
Silicate (TEOS), C 2HFiveOH, H2O and H
Cl was stirred and mixed at 60 ° C. for 1.5 hours to obtain a solution.
To 0.05M NHFourImmediately after adding OH, spin coating
Machine applies the solution to the chip and NHFourAddition of OH
Accelerates gelation rate, where NHFourAddition rate of OH
Is 1/10 of the solution volume, and a chip coated with a gel film
At 37 ° C for 24 hours in an atmosphere containing saturated ethanol gas
Place and allow the membrane to age, then change the pressure
A method to remove the solvent inside and form a porous membrane is described.
ing. At this time, the pressure during the process is 1 atmospheric pressure or less,
Change solvent from liquid to gas, that is, supercritical state of solvent
Compress solvent under high pressure close to normal or supercritical conditions
A cavity is formed by removing it as gas. this
Both of these processes require careful control and excess membranes.
You have to avoid the shrinkage effect
Absent. Porous volume ratio of the membrane obtained by the above method, diameter,
The distribution varies depending on the reaction conditions and the type of solvent.
Generally, the volume of porosity in the membrane is about 20% to 95%, preferably
It is preferably 75% or more, and the average diameter is about 80 nm or less,
It is preferably 2 nm to 25 nm, and the porosity has a volume of 8 nm.
When occupying 0%, the material dielectric constant is about 1.5 or less.
Here, the larger the occupied volume ratio of the porous material in the membrane, the surface
Poor adhesion and heat resistance. Therefore, after that
The upper and lower layers of the porous membrane are usually
Then, an adhesive layer is provided by CVD. In layers like this
Therefore, the adhesive effect is enhanced, and further, the material can be put into the porous body.
It has the effect of preventing water absorption or transition exudation of atoms.
【００１０】その他に、膜形成材料にある特定の物質を
混合させ、膜形成後にその物質を除去することにより多
孔質膜を形成する方法がある（膜内混合物による方
法）。例えば米国特許第５，７４４，３９９号によれ
ば、ＳｉＯ2による膜形成工程において、フラーレン混
合物で薄膜を形成した後、溶媒でフラーレンを溶解す
る、またはＯ2またはＯ3プラズマでフラーレンをＣＯ2
に酸化することによって多孔質膜を形成する。ここでフ
ラーレンとは、３２〜９６０個の炭素原子を含み、測地
線ドーム構造をしている物質である。In addition, there is a method of forming a porous film by mixing a specific substance with a film forming material and removing the substance after forming the film (a method using an in-film mixture). For example, according to US Pat. No. 5,744,399, in a film forming process using SiO 2 , after forming a thin film with a fullerene mixture, the fullerene is dissolved with a solvent, or the fullerene is converted into CO 2 with O 2 or O 3 plasma.
A porous film is formed by oxidization. Here, the fullerene is a substance containing 32 to 960 carbon atoms and having a geodesic dome structure.
【００１１】また米国特許第５，７８５，７８７号によ
れば、ＵＶ分解性の材料、または低温で加熱昇華する材
料（例えばアントロキノン、低融点ワックス等）を、ポ
リテトラフルオロエチレン（ＰＴＦＥ）膜の混合物とし
て用いている。得られた７０％多孔性のＰＴＦＥ膜は、
誘電率を従来の１．９から１．２に低下させている。し
かしながら、このような多孔構造を有する膜はそのまま
では基材から剥離しやすいため、上下に接着層が必要で
ある。According to US Pat. No. 5,785,787, a polytetrafluoroethylene (PTFE) film is prepared by using a UV decomposable material or a material that sublimates by heating at a low temperature (for example, anthroquinone, low melting point wax, etc.). Used as a mixture of. The resulting 70% porous PTFE membrane is
The permittivity is lowered from 1.9 in the past to 1.2. However, since the film having such a porous structure is easily peeled off from the base material as it is, an adhesive layer is required above and below.
【００１２】このように、半導体製造工程に適用される
低誘電性の多孔性誘電膜の形成は、上述した溶媒揮発ま
たは膜内混合物除去によるものが大半である。しかしな
がら、前者は、多孔質膜の収縮、基材との弱い接着性と
いう問題があり、後者は、膜内混合物が残留し、後処理
工程で滲出すという問題がある。従って、溶媒を用いな
い低誘電性の多孔性誘電膜の形成方法が求められてい
る。As described above, the formation of the low dielectric porous dielectric film applied to the semiconductor manufacturing process is mostly performed by the above-described solvent volatilization or removal of the in-film mixture. However, the former has a problem that the porous film shrinks and weakly adheres to the substrate, and the latter has a problem that the mixture in the film remains and exudes in the post-treatment process. Therefore, there is a demand for a method of forming a low dielectric porous dielectric film that does not use a solvent.
【００１３】[0013]
【発明が解決しようとする課題】本発明の目的は、従来
の低誘電性の多孔性誘電膜の製造方法に起因する有機溶
媒残留、膜内混合物の遷移、多孔質膜の低い接着性、溶
媒揮発工程で発生するサイズ収縮等の問題を解決するた
めに、溶媒を用いない低誘電性の多孔性誘電膜の製造方
法を提供することである。DISCLOSURE OF THE INVENTION It is an object of the present invention to retain an organic solvent due to a conventional method for producing a low dielectric porous dielectric film, transition of an in-membrane mixture, low adhesion of a porous film, and a solvent. It is an object of the present invention to provide a method for producing a low dielectric porous dielectric film that does not use a solvent in order to solve problems such as size shrinkage that occur in the volatilization process.
【００１４】[0014]
【課題を解決するための手段】すなわち本発明は、半導
体基材に誘電膜を形成する工程（Ａ）と、該半導体基材
を高圧不活性ガスの雰囲気に入れる工程（Ｂ）と、該雰
囲気の圧力を解除し、該誘電膜の表面に孔洞を形成させ
る工程（Ｃ）とを含む、低誘電性の多孔性誘電膜の製造
方法である。That is, the present invention provides a step (A) of forming a dielectric film on a semiconductor substrate, a step (B) of placing the semiconductor substrate in an atmosphere of a high pressure inert gas, and the atmosphere. And a step of forming pores on the surface of the dielectric film (C).
【００１５】さらに本発明は、工程（Ａ）〜工程（Ｃ）
を、所望の厚さの誘電膜が得られるまで繰り返して行
う、前記製造方法である。Furthermore, the present invention provides the steps (A) to (C).
Is repeatedly performed until a dielectric film having a desired thickness is obtained.
【００１６】さらに本発明は、工程（Ｂ）において、誘
電膜が形成された該半導体基材を高圧タンク内に入れ、
高圧不活性ガスを該高圧タンク内に導入する、前記製造
方法である。Further, in the present invention, in the step (B), the semiconductor substrate having the dielectric film formed thereon is placed in a high pressure tank,
In the above-mentioned manufacturing method, a high-pressure inert gas is introduced into the high-pressure tank.
【００１７】さらに本発明は、該高圧不活性ガスは、該
誘電膜と反応しない物質からなる、前記製造方法であ
る。Further, the present invention is the above-mentioned manufacturing method, wherein the high-pressure inert gas is made of a substance that does not react with the dielectric film.
【００１８】さらに本発明は、該高圧不活性ガスは、二
酸化炭素、窒素、ヘリウム、アルゴン、エタン、プロパ
ン、エチレン、プロペン、またはそれらの混合ガスであ
る、前記製造方法である。Further, the present invention is the above-mentioned production method, wherein the high-pressure inert gas is carbon dioxide, nitrogen, helium, argon, ethane, propane, ethylene, propene, or a mixed gas thereof.
【００１９】さらに本発明は、該誘電膜は、ＣＶＤで形
成された低誘電性無機材料膜、または、回転塗布で形成
された低誘電有機高分子膜である、前記製造方法であ
る。Further, the present invention is the above-mentioned manufacturing method, wherein the dielectric film is a low dielectric inorganic material film formed by CVD or a low dielectric organic polymer film formed by spin coating.
【００２０】さらに本発明は、該無機材料膜は、ＳｉＯ
Ｆ、α−ＣＦ、またはＳｉＯＣである、前記製造方法で
ある。Further, in the present invention, the inorganic material film is made of SiO 2.
The production method is F, α-CF, or SiOC.
【００２１】さらに本発明は、該有機高分子膜は、ポリ
イミドまたはポリテトラフルオロエチレンからなる、前
記製造方法である。Further, the present invention is the above-mentioned manufacturing method, wherein the organic polymer film is made of polyimide or polytetrafluoroethylene.
【００２２】さらに本発明は、該高圧不活性ガスは、該
高圧不活性ガスの臨界圧力近傍または臨界圧力を超過し
た圧力である、前記製造方法である。Further, the present invention is the above-mentioned manufacturing method, wherein the high-pressure inert gas has a pressure near or above the critical pressure of the high-pressure inert gas.
【００２３】さらに本発明は、該高圧不活性ガスは、該
高圧不活性ガスの臨界温度近傍または臨界温度を超過し
た温度である、前記製造方法である。Further, the present invention is the above-mentioned production method, wherein the high-pressure inert gas has a temperature near or above the critical temperature of the high-pressure inert gas.
【００２４】さらに本発明は、該高圧不活性ガスは超臨
界流体である、前記製造方法である。Further, the present invention is the above-mentioned manufacturing method, wherein the high-pressure inert gas is a supercritical fluid.
【００２５】さらに本発明は、工程（Ｃ）において、
０．３〜７．５ａｔｍ／秒の減圧速度で、該雰囲気の圧
力を下げる、請求項１〜１１のいずれか一項に記載の製
造方法。Furthermore, in the present invention, in the step (C),
The manufacturing method according to any one of claims 1 to 11, wherein the pressure of the atmosphere is reduced at a pressure reduction rate of 0.3 to 7.5 atm / sec.
【００２６】さらに本発明は、該孔洞は、直径範囲が５
〜８０ｎｍである、前記製造方法である。Further, in the present invention, the hole cavity has a diameter range of 5
It is the said manufacturing method which is -80 nm.
【００２７】さらに本発明は、該孔洞は、直径範囲が５
〜５０ｎｍである、前記製造方法である。Further, in the present invention, the hole cavity has a diameter range of 5
It is the said manufacturing method which is-50 nm.
【００２８】[0028]
【発明の実施の形態】本発明の低誘電性の多孔性誘電膜
の製造方法は、半導体基材に誘電膜を形成する工程
（Ａ）と、該半導体基材を高圧不活性ガスの雰囲気に入
れる工程（Ｂ）と、該雰囲気の圧力を解除し、該誘電膜
の表面に孔洞を形成させる工程（Ｃ）とを含むものであ
る。BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a low dielectric porous dielectric film of the present invention comprises a step (A) of forming a dielectric film on a semiconductor substrate and exposing the semiconductor substrate to a high pressure inert gas atmosphere. It includes a step (B) of putting in and a step (C) of releasing the pressure of the atmosphere to form a cavity on the surface of the dielectric film.
【００２９】本発明の製造方法を、図を参照しながら以
下に説明する。図１ａは、本発明の方法の主な工程
（Ａ）〜（Ｃ）のフローチャートである。図１ｂは、図
１ａフローチャートの工程ごとの半導体基板断面図であ
る。The manufacturing method of the present invention will be described below with reference to the drawings. FIG. 1a is a flow chart of the main steps (A)-(C) of the method of the invention. 1b is a sectional view of the semiconductor substrate in each step of the flowchart of FIG. 1a.
【００３０】工程（Ａ）において、当業界周知の技術を
用いて誘電膜を半導体基材上に形成する。好ましくは、
該誘電膜は、ＣＶＤで形成された低誘電性無機材料膜、
または、回転塗布で形成された低誘電有機高分子膜であ
り、用いる膜形成素材によって適宜選択される。用いら
れ得る誘電膜として、好ましくは、ＣＶＤで蒸着される
低誘電性無機材料膜であり、例えばＳｉＯＦ、α−Ｃ
Ｆ、ＳｉＯＣである。ここでα−ＣＦとは、フッ素化ア
モルファス炭素（ａ−Ｆ：Ｃとも記載される）のことで
ある。同様に好ましくは回転塗布で形成された低誘電有
機高分子膜であり、例えばポリイミド、ポリテトラフル
オロエチレン（ＰＴＦＥ）が好適に使用されうる。In step (A), a dielectric film is formed on the semiconductor substrate using a technique well known in the art. Preferably,
The dielectric film is a low dielectric inorganic material film formed by CVD,
Alternatively, it is a low dielectric organic polymer film formed by spin coating, and is appropriately selected depending on the film forming material used. The dielectric film that can be used is preferably a low dielectric inorganic material film deposited by CVD, such as SiOF or α-C.
F and SiOC. Here, α-CF is fluorinated amorphous carbon (also described as aF: C). Similarly, it is preferably a low dielectric organic polymer film formed by spin coating, and for example, polyimide or polytetrafluoroethylene (PTFE) can be preferably used.
【００３１】次に工程（Ｂ）において、該半導体基材を
高圧不活性ガスの雰囲気に入れるが、ここで好ましく
は、高圧タンク内に入れ、高圧不活性ガスを導入する方
法が使用されうる。これにより高圧不活性ガスは、形成
された誘電膜の表面に染み込む。ここで高圧不活性ガス
の圧力は、そのガスの臨界圧力近傍または超過した圧力
であり、具体的には、該臨界圧力の０．９〜２．５倍の
範囲内であることが好ましい。同様に、高圧不活性ガス
の温度は、そのガスの臨界温度近傍または超過した温度
であることが好ましい。より好ましくは、高圧不活性ガ
スは超臨界流体である。超臨界流体とは、圧力、温度
が、気−液間の相平衡における臨界点を超えた状態の流
体のことをいう。Next, in the step (B), the semiconductor substrate is placed in an atmosphere of high-pressure inert gas, and preferably, a method of placing it in a high-pressure tank and introducing the high-pressure inert gas can be used. As a result, the high-pressure inert gas permeates the surface of the formed dielectric film. Here, the pressure of the high-pressure inert gas is a pressure near or exceeding the critical pressure of the gas, and specifically, it is preferably within a range of 0.9 to 2.5 times the critical pressure. Similarly, the temperature of the high pressure inert gas is preferably near or above the critical temperature of the gas. More preferably, the high pressure inert gas is a supercritical fluid. The supercritical fluid is a fluid in which the pressure and temperature exceed the critical point in the gas-liquid phase equilibrium.
【００３２】上記高圧不活性ガスとして用いられ得るガ
スは、好ましくは誘電膜と反応しないガスからなるもの
である。さらに好ましくは、臨界温度（Ｔc）および臨
界圧力（Ｐc）とともに示せば、二酸化炭素（Ｔc＝３
１．１℃，Ｐc＝７２．７６ａｔｍ）、窒素（Ｔc＝−１
４７℃，Ｐc＝３３．４４ａｔｍ）、ヘリウム（Ｔc＝−
２６９．９℃，Ｐc＝１．１２ａｔｍ）、アルゴン（Ｔc
＝−１２２．４℃，Ｐ c＝４８．０３ａｔｍ）、エタン
（Ｔc＝−３２．２℃，Ｐc＝４８．１６ａｔｍ）、プロ
パン（Ｔc＝９６．７℃，Ｐc＝４１．８７ａｔｍ）、エ
チレン（Ｔc＝９．９℃，Ｐc＝５０．４６ａｔｍ）、プ
ロペン（Ｔc＝９１．９℃，Ｐc＝４５．３７ａｔｍ）な
どのガス、またはこれらの混合ガスである。A gas that can be used as the high-pressure inert gas.
The gas preferably comprises a gas that does not react with the dielectric film.
Is. More preferably, the critical temperature (Tc) And Rin
Field pressure (Pc), Carbon dioxide (Tc= 3
1.1 ° C, Pc= 72.76 atm), nitrogen (Tc= -1
47 ° C, Pc= 33.44 atm), helium (Tc=-
269.9 ° C, Pc= 1.12 atm), argon (Tc
= -122.4 ° C, P c= 48.03 atm), ethane
(Tc= -32.2 ° C, Pc= 48.16 atm), professional
Bread (Tc= 96.7 ° C, Pc= 41.87 atm), d
Chilen (Tc= 9.9 ° C, Pc= 50.46 atm),
Lopen (Tc= 91.9 ° C, Pc= 45.37 atm)
Which gas or a mixed gas of these.
【００３３】一定時間の後、高圧タンク内の圧力を迅速
に解除することにより、誘電膜の表面に孔洞を形成す
る。高圧不活性ガスまたはその超臨界流体の誘電膜への
浸透力によって、連続且つ緻密に孔洞が誘電膜の表面に
形成され、これは誘電膜と基材との間の接着に影響を与
えない。After a certain period of time, the pressure in the high pressure tank is rapidly released to form a cavity in the surface of the dielectric film. The osmotic force of the high-pressure inert gas or its supercritical fluid into the dielectric film continuously and densely forms pores on the surface of the dielectric film, which does not affect the adhesion between the dielectric film and the substrate.
【００３４】高圧不活性ガスが膜表面下層に拡散した
後、迅速に圧力を解除すると、高圧不活性ガスは急速な
圧力低下によりガス膨張を起こすために、誘電膜表面に
孔洞が形成する。この際、減圧変化の範囲は、好ましく
は０．３〜７．５ａｔｍ／秒、より好ましくは１．０〜
４．０ａｔｍ／秒である。ここで０．３ａｔｍ／秒未満
の場合、多孔質構造が形成され難いため好ましくない。
上限については、使用する排気パイプの強度が耐えうる
範囲であれば特に限定されないが、通常は７．５ａｔｍ
／秒以下であることが好ましい。When the high-pressure inert gas diffuses to the lower layer of the film surface and then the pressure is rapidly released, the high-pressure inert gas causes a gas expansion due to a rapid pressure drop, so that a pore is formed on the surface of the dielectric film. At this time, the range of change in reduced pressure is preferably 0.3 to 7.5 atm / sec, more preferably 1.0 to
It is 4.0 atm / sec. If it is less than 0.3 atm / sec, it is difficult to form a porous structure, which is not preferable.
The upper limit is not particularly limited as long as the strength of the exhaust pipe used can withstand, but is usually 7.5 atm.
/ Sec or less is preferable.
【００３５】本発明の高圧膜処理工程は、圧力の解除速
度を制御することによって、多様な多孔質の直径分布を
形成することができる。すなわち、圧力解除速度が大き
いほど、直径が大きい多孔質の比例が大きくなる。多孔
質の直径範囲は、好ましくは直径約５ｎｍ〜８０ｎｍ、
より好ましくは５ｎｍ〜５０ｎｍ、さらにより好ましく
は５ｎｍ〜２０ｎｍである。In the high-pressure membrane treatment process of the present invention, various pore diameter distributions can be formed by controlling the pressure release rate. That is, the greater the pressure release rate, the greater the proportion of the larger diameter porous material. The diameter range of the porous layer is preferably about 5 nm to 80 nm in diameter,
It is more preferably 5 nm to 50 nm, and even more preferably 5 nm to 20 nm.
【００３６】このようにガスエントロピー変化により生
じたエネルギーによって膜に孔洞を形成する方法は、次
のような利点がある。まず、高圧条件下の緻密ガス、ま
たは、気体および液体両相の超臨界流体によって多孔性
の誘電膜を製作するので、溶媒による汚染の問題がな
い。すなわち、溶媒を用いないので、溶媒揮発による膜
収縮や、後処理工程中の膜内混合物が表面に滲み出すと
いう従来の問題を解消することができる。また、ゾル−
ゲル方式の多孔質膜製造法に比べ、本発明は膜ゲル化、
熟成および溶媒揮発等の複雑な操作条件や工程を簡素化
することができる。さらに、本発明の低誘電性の多孔性
誘電膜は、膜表面のみに連続かつ緻密な孔洞を形成する
ので、膜と基材との接着能力を低めない。The method of forming a cavity in the film by the energy generated by the gas entropy change has the following advantages. First, since a porous dielectric film is manufactured using a dense gas under high pressure conditions or a supercritical fluid in both gas and liquid phases, there is no problem of solvent contamination. That is, since the solvent is not used, it is possible to solve the conventional problems that the film shrinks due to the solvent volatilization and the in-membrane mixture in the post-treatment step oozes to the surface. Also, the sol
Compared with the gel type porous membrane manufacturing method, the present invention is a membrane gelation,
It is possible to simplify complicated operating conditions and steps such as aging and solvent evaporation. Furthermore, since the low dielectric porous dielectric film of the present invention forms continuous and dense pores only on the film surface, the adhesive ability between the film and the base material is not deteriorated.
【００３７】また、上記工程（Ａ）〜工程（Ｃ）を所望
する誘電膜厚さになるまで繰り返して行うことにより、
膜体積に対する多孔質の所望する占有体積率が達成され
得る（図１ａにおける「多層積層」のサイクル）。By repeating the above steps (A) to (C) until the desired dielectric film thickness is obtained,
The desired occupancy volume ratio of porosity to membrane volume can be achieved (cycle of "multilayer stacking" in Figure Ia).
【００３８】以上説明した本発明の製造方法は、従来の
各種低誘電率材料（ｋ＜４．１）からなる多孔質膜形成
に適用することができる。例えば、２０００ÅのＳｉ−
Ｏ−Ｃ−Ｆ膜にアルゴンガスの超臨界条件で多孔質を形
成する場合は、多孔質の直径範囲が５ｎｍ〜８０ｎｍの
誘電膜を形成することができる。その内、全孔の約７０
％を占める主な多孔質の直径範囲は５ｎｍ〜５０ｎｍ、
好ましくは５ｎｍ〜２０ｎｍである。多孔質形成前の膜
のｋ値は２．５〜２．８であるが、本発明の多孔質形成
後は約２．２〜２．６になり誘電率を低くすることがで
きる。さらに膜の多孔質率を増すと、ｋ値をさらに低め
ることができる。The manufacturing method of the present invention described above can be applied to the formation of a porous film made of various conventional low dielectric constant materials (k <4.1). For example, 2000Å Si-
When the O-C-F film is formed into a porous film under a supercritical condition of argon gas, a dielectric film having a porous diameter range of 5 nm to 80 nm can be formed. Among them, about 70 of all holes
%, The main porous diameter range is 5 nm to 50 nm,
It is preferably 5 nm to 20 nm. The k value of the film before the formation of the porosity is 2.5 to 2.8, but after the formation of the porosity of the present invention, it is about 2.2 to 2.6, and the dielectric constant can be lowered. Further increasing the porosity of the membrane can further reduce the k value.
【００３９】次に、本発明の低誘電性の多孔性誘電膜製
造方法を実施する装置について説明する。図２は、一般
的に用いられうるマルチチャンバークラスターツールシ
ステム１０（昌研科技股ふん有限公司社製、NARC CT-00
1）の概略図である。図中、高圧不活性ガスを備える蓄
圧タンク１８、蓄圧タンク１８と接続される高圧タンク
１２、高圧タンク１２に接続されるＣＶＤまたはエッチ
ングを行うための反応室１４、半導体チップの運搬など
に用いられる機械アーム１６が記載されている。もちろ
んこの装置に限らず、従来の装置をそのまま、または改
変を施すことによって本発明に用いることができる。Next, an apparatus for carrying out the method for producing a low dielectric porous dielectric film of the present invention will be described. FIG. 2 shows a commonly-used multi-chamber cluster tool system 10 (manufactured by Shoken Science & Technology Co., Ltd., NARC CT-00).
It is a schematic diagram of 1). In the figure, a pressure accumulating tank 18 provided with a high pressure inert gas, a high pressure tank 12 connected to the pressure accumulating tank 18, a reaction chamber 14 connected to the high pressure tank 12 for performing CVD or etching, and used for transporting semiconductor chips and the like. A mechanical arm 16 is described. Of course, not only this device but also a conventional device can be used in the present invention as it is or by modifying it.
【００４０】[0040]
【実施例】以下に、実施例により本発明をより詳細に説
明する。下記の実施例１〜８はすべて、もとの誘電膜と
してＳｉＨ4＋Ｎ2Ｏ＋ＣＦ4等から選択されてなるガス
をＣＶＤで蒸着させたＳｉ−Ｏ−Ｃ−Ｆ低誘電膜を用い
ており、この誘電膜の誘電率は、約２．８であった。The present invention will be described in more detail below with reference to examples. All Examples 1-8 below, uses a Si-O-CF low dielectric film was deposited a gas consisting selected from SiH 4 + N 2 O + CF 4 or the like as original dielectric film CVD, The dielectric constant of this dielectric film was about 2.8.
【００４１】［実施例１］コンプレッサーを起動し、超
高純度のアルゴンを予め増圧し、蓄圧タンクに貯存し、
蓄圧タンクの圧力を１７０ａｔｍに設定した。[Example 1] The compressor was started up, the pressure of ultra-high purity argon was increased in advance, and the pressure was stored in the accumulator tank.
The pressure of the accumulator tank was set to 170 atm.
【００４２】ＣＶＤによって２０００ÅのＳｉ−Ｏ−Ｃ
−Ｆ誘電膜を積層したチップを、体積が１Ｌで、６８０
ａｔｍまで耐圧できるステンレス圧力タンクに入れ、４
０℃まで加熱した。次に、瞬間的に蓄圧タンク中のアル
ゴンを反応タンクに導入し、圧力を６８ａｔｍにコント
ロールした。１５分後、毎秒４．０８ａｔｍで反応タン
ク内の圧力を解除した。得られた多孔質の直径範囲は５
ｎｍ〜７０ｎｍであり、その内、主な多孔質（すなわ
ち、全孔洞の約７０％）の直径範囲は５ｎｍ〜４０ｎｍ
であった。2000Å Si-O-C by CVD
A chip in which a -F dielectric film is laminated has a volume of 1 L and is 680
Put in a stainless steel pressure tank that can withstand up to atm, 4
Heated to 0 ° C. Next, the argon in the accumulator tank was instantaneously introduced into the reaction tank, and the pressure was controlled to 68 atm. After 15 minutes, the pressure in the reaction tank was released at 4.08 atm / s. The resulting porous diameter range is 5
nm to 70 nm, of which the major porous (ie, about 70% of all pores) diameter range is 5 nm to 40 nm
Met.
【００４３】［実施例２］反応圧力が６８ａｔｍ、温度
が４０℃、反応時間が３０分、毎秒４．０８ａｔｍで反
応タンク内の圧力を解除し対外は、実施例１と同じ反応
を行ったところ、多孔質の直径範囲は５ｎｍ〜８０ｎｍ
であり、その内、主な多孔質の直径範囲は５ｎｍ〜６０
ｎｍであった。Example 2 The reaction pressure was 68 atm, the temperature was 40 ° C., the reaction time was 30 minutes, the pressure in the reaction tank was released at 4.08 atm / s, and the same reaction as in Example 1 was performed outside. , Porous diameter range is 5 nm to 80 nm
And the diameter range of the main porous is 5 nm to 60
was nm.
【００４４】［実施例３］反応圧力が１０８．８ａｔ
ｍ、温度が４０℃、反応時間が３０分、毎秒１．０２ａ
ｔｍで反応タンク内の圧力を解除した以外は実施例１と
同じ反応を行ったところ、多孔質の直径範囲は５ｎｍ〜
７０ｎｍであり、その内、主な多孔質の直径範囲は５ｎ
ｍ〜５０ｎｍであった。[Example 3] Reaction pressure was 108.8 at
m, temperature 40 ° C., reaction time 30 minutes, 1.02 a / s
When the same reaction as in Example 1 was performed except that the pressure in the reaction tank was released at tm, the diameter range of the porous material was 5 nm to
70 nm, of which the main porous diameter range is 5 n
It was m to 50 nm.
【００４５】［実施例４］反応圧力が１０８．８ａｔ
ｍ、温度が４０℃、反応時間が３０分、毎秒４．０８ａ
ｔｍで反応タンク内の圧力を解除した以外は実施例１と
同じ反応を行ったところ、多孔質の直径範囲は５ｎｍ〜
８０ｎｍであり、その内、主な多孔質の直径範囲は５ｎ
ｍ〜６０ｎｍであった。Example 4 The reaction pressure was 108.8 at.
m, temperature 40 ° C., reaction time 30 minutes, 4.08 a / s
When the same reaction as in Example 1 was performed except that the pressure in the reaction tank was released at tm, the diameter range of the porous material was 5 nm to
80 nm, of which the main porous diameter range is 5 n
It was m-60 nm.
【００４６】［実施例５］反応圧力が１０８．８ａｔ
ｍ、温度が４０℃、反応時間が３０分、毎秒４．０８ａ
ｔｍで反応タンク内の圧力を解除した以外は実施例１と
同じ反応を行ったところ、多孔質の直径範囲は５ｎｍ〜
９０ｎｍであり、その内、主な多孔質の直径範囲は１０
ｎｍ〜６０ｎｍであった。Example 5 The reaction pressure was 108.8 at.
m, temperature 40 ° C., reaction time 30 minutes, 4.08 a / s
When the same reaction as in Example 1 was performed except that the pressure in the reaction tank was released at tm, the diameter range of the porous material was 5 nm to
90 nm, of which the major porous diameter range is 10
It was nm to 60 nm.
【００４７】［実施例６］反応圧力が８８．４ａｔｍ、
温度が４０℃、反応時間が３０分、毎秒２．０４ａｔｍ
で反応タンク内の圧力を解除した以外は実施例１と同じ
反応を行ったところ、多孔質の直径範囲は５ｎｍ〜８０
ｎｍであり、その内、主な多孔質の直径範囲は５ｎｍ〜
５０ｎｍであった。Example 6 The reaction pressure was 88.4 atm,
Temperature 40 ° C, reaction time 30 minutes, 2.04 atm / s
When the same reaction as in Example 1 was carried out except that the pressure in the reaction tank was released in step 1, the porous diameter range was 5 nm to 80 nm.
nm, of which the main porous diameter range is 5 nm to
It was 50 nm.
【００４８】［実施例７］反応圧力が８８．４ａｔｍ、
温度が４０℃、反応時間が１５分、毎秒２．０４ａｔｍ
で反応タンク内の圧力を解除した以外は実施例１と同じ
反応を行ったところ、多孔質の直径範囲は５ｎｍ〜８０
ｎｍであり、その内、主な多孔質の直径範囲は５ｎｍ〜
４０ｎｍであった。Example 7 The reaction pressure was 88.4 atm,
Temperature 40 ° C, reaction time 15 minutes, 2.04 atm / s
When the same reaction as in Example 1 was carried out except that the pressure in the reaction tank was released in 1., the diameter range of the porous material was 5 nm to 80 nm.
nm, of which the main porous diameter range is 5 nm to
It was 40 nm.
【００４９】［実施例８］反応圧力が８８．４ａｔｍ、
温度が４０℃、反応時間が１５分、毎秒４．０８ａｔｍ
で反応タンク内の圧力を解除した以外は実施例１と同じ
反応を行ったところ、多孔質の直径範囲は５ｎｍ〜８０
ｎｍであり、その内、主な多孔質の直径範囲は５ｎｍ〜
５０ｎｍであった。Example 8 The reaction pressure was 88.4 atm,
Temperature 40 ° C, reaction time 15 minutes, 4.08 atm / s
When the same reaction as in Example 1 was carried out except that the pressure in the reaction tank was released in step 1, the porous diameter range was 5 nm to 80 nm.
nm, of which the main porous diameter range is 5 nm to
It was 50 nm.
【００５０】上記実施例１〜８で得られた誘電膜の誘電
率を測定したところ、もとの誘電率約２．８から、いず
れも２．６程度にまで誘電率を低めることができた。When the dielectric constants of the dielectric films obtained in the above Examples 1 to 8 were measured, the dielectric constant could be lowered from the original dielectric constant of about 2.8 to about 2.6 in all cases. .
【００５１】[0051]
【発明の効果】本発明の低誘電性の多孔性誘電膜の製造
方法は、次のような利点がある。
（１）高圧不活性ガスまたは超臨界流体によって多孔性
の誘電膜を形成するので、溶媒による汚染、溶媒揮発に
よる膜収縮、後処理工程中に膜内混合物が表面に滲み出
すという従来の問題を解消することができる。
（２）従来のゾル−ゲル方式の多孔質膜製造法に比べ、
膜ゲル化、熟成および溶媒揮発等の複雑な操作条件や工
程を簡素化することができる。
（３）膜表面のみに連続かつ緻密な孔洞を形成するの
で、膜と基材との接着能力を低めない。The method for producing a low dielectric porous dielectric film of the present invention has the following advantages. (1) Since a porous dielectric film is formed by a high-pressure inert gas or a supercritical fluid, the conventional problems of contamination by a solvent, film shrinkage due to volatilization of the solvent, and exudation of an in-membrane mixture on the surface during a post-treatment process are solved. It can be resolved. (2) Compared with the conventional sol-gel type porous membrane manufacturing method,
It is possible to simplify complicated operating conditions and steps such as film gelation, aging and solvent volatilization. (3) Since the continuous and dense pores are formed only on the surface of the film, the adhesive ability between the film and the base material is not deteriorated.
【図１】 図１ａは、本発明の工程（Ａ）〜（Ｃ）を示
すフローチャートである。図１ｂは、図１ａのフローチ
ャートの各工程における半導体基板の断面図を示す。FIG. 1a is a flowchart showing steps (A) to (C) of the present invention. FIG. 1b is a sectional view of the semiconductor substrate in each step of the flowchart of FIG. 1a.
【図２】 本発明の方法を実施するためのマルチチャン
バークラスターツールシステム１０の概略図である。FIG. 2 is a schematic diagram of a multi-chamber cluster tool system 10 for performing the method of the present invention.
１０…マルチチャンバークラスターツールシステム １２…高圧タンク １４…ＣＶＤまたはエッチング反応室 １６…機械アーム １８…蓄圧タンク 10 ... Multi-chamber cluster tool system 12 ... High pressure tank 14 ... CVD or etching reaction chamber 16 ... Mechanical arm 18 ... Accumulation tank
フロントページの続き Ｆターム(参考） 5F033 QQ86 RR01 RR11 RR21 RR22 SS11 SS21 XX24 XX25 5F058 AA10 AC02 AC05 AF04 AG10 BA20 BF02 BH20 Continued front page F term (reference) 5F033 QQ86 RR01 RR11 RR21 RR22 SS11 SS21 XX24 XX25 5F058 AA10 AC02 AC05 AF04 AG10 BA20 BF02 BH20
Claims (14)
（Ａ）と、 該半導体基材を高圧不活性ガスの雰囲気に入れる工程
（Ｂ）と、 該雰囲気の圧力を解除し、該誘電膜の表面に孔洞を形成
させる工程（Ｃ）とを含む、低誘電性の多孔性誘電膜の
製造方法。1. A step (A) of forming a dielectric film on a semiconductor base material, a step (B) of placing the semiconductor base material in an atmosphere of a high-pressure inert gas, and releasing the pressure of the atmosphere to release the dielectric film. And a step (C) of forming pores on the surface of the porous ceramic film.
の誘電膜が得られるまで繰り返して行う、請求項１に記
載の製造方法。2. The manufacturing method according to claim 1, wherein steps (A) to (C) are repeated until a dielectric film having a desired thickness is obtained.
た該半導体基材を高圧タンク内に入れ、高圧不活性ガス
を該高圧タンク内に導入する、請求項１または２に記載
の製造方法。3. The production according to claim 1, wherein in the step (B), the semiconductor substrate having the dielectric film formed thereon is placed in a high pressure tank, and a high pressure inert gas is introduced into the high pressure tank. Method.
ない物質からなる、請求項１〜３のいずれか一項に記載
の製造方法。4. The manufacturing method according to claim 1, wherein the high-pressure inert gas is made of a substance that does not react with the dielectric film.
素、ヘリウム、アルゴン、エタン、プロパン、エチレ
ン、プロペン、またはそれらの混合ガスである、請求項
４に記載の製造方法。5. The manufacturing method according to claim 4, wherein the high-pressure inert gas is carbon dioxide, nitrogen, helium, argon, ethane, propane, ethylene, propene, or a mixed gas thereof.
性無機材料膜、または、回転塗布で形成された低誘電有
機高分子膜である、請求項１〜５のいずれか一項に記載
の製造方法。6. The low dielectric organic material film formed by CVD or the low dielectric organic polymer film formed by spin coating according to claim 1, wherein the dielectric film is a low dielectric inorganic material film. The manufacturing method described.
またはＳｉＯＣである、請求項６記載の製造方法。7. The inorganic material film comprises SiOF, α-CF,
Alternatively, the manufacturing method according to claim 6, which is SiOC.
リテトラフルオロエチレンからなる、請求項６に記載の
製造方法。8. The method according to claim 6, wherein the organic polymer film is made of polyimide or polytetrafluoroethylene.
の臨界圧力近傍または臨界圧力を超過した圧力である、
請求項１〜８のいずれか一項に記載の製造方法。9. The high-pressure inert gas has a pressure near or above the critical pressure of the high-pressure inert gas,
The manufacturing method according to claim 1.
スの臨界温度近傍または臨界温度を超過した温度であ
る、請求項１〜９のいずれか一項に記載の製造方法。10. The production method according to claim 1, wherein the high-pressure inert gas has a temperature near or above the critical temperature of the high-pressure inert gas.
る、請求項１〜１０のいずれか一項に記載の製造方法。11. The manufacturing method according to claim 1, wherein the high-pressure inert gas is a supercritical fluid.
ａｔｍ／秒の減圧速度で、該雰囲気の圧力を下げる、請
求項１〜１１のいずれか一項に記載の製造方法。12. In the step (C), 0.3 to 7.5.
The manufacturing method according to claim 1, wherein the pressure of the atmosphere is reduced at a pressure reduction rate of atm / sec.
ある、請求項１〜１２のいずれか一項に記載の製造方
法。13. The manufacturing method according to claim 1, wherein the hole cavity has a diameter range of 5 to 80 nm.
ある、請求項１３に記載の製造方法。14. The manufacturing method according to claim 13, wherein the hole cavity has a diameter range of 5 to 50 nm.
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| KR20160117288A (en) * | 2015-03-31 | 2016-10-10 | 램 리써치 코포레이션 | Cyclical, non-isobaric, pore sealing method to prevent precursor penetration into the substrate |
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| KR20160117288A (en) * | 2015-03-31 | 2016-10-10 | 램 리써치 코포레이션 | Cyclical, non-isobaric, pore sealing method to prevent precursor penetration into the substrate |
| KR102436980B1 (en) | 2015-03-31 | 2022-08-25 | 램 리써치 코포레이션 | Cyclical, non-isobaric, pore sealing method to prevent precursor penetration into the substrate |
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